EP1615971B2 - Water dispersible polythiophenes made with polymeric acid colloids - Google Patents

Water dispersible polythiophenes made with polymeric acid colloids Download PDF

Info

Publication number
EP1615971B2
EP1615971B2 EP20040750548 EP04750548A EP1615971B2 EP 1615971 B2 EP1615971 B2 EP 1615971B2 EP 20040750548 EP20040750548 EP 20040750548 EP 04750548 A EP04750548 A EP 04750548A EP 1615971 B2 EP1615971 B2 EP 1615971B2
Authority
EP
Grant status
Grant
Patent type
Prior art keywords
acid
layer
embodiment
ether
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP20040750548
Other languages
German (de)
French (fr)
Other versions
EP1615971A2 (en )
EP1615971B1 (en )
Inventor
Che-Hsiung Hsu
Yong Cao
Sunghan Kim
Daniel David Lecloux
Huawen Li
Charles Douglas Macpherson
Chi Zhang
Hjalti Skulason
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
E I du Pont de Nemours and Co
Original Assignee
E I du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date
Family has litigation

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/48Conductive polymers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/54Electrolytes
    • H01G11/56Solid electrolytes, e.g. gels; Additives therein
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0032Selection of organic semiconducting materials, e.g. organic light sensitive or organic light emitting materials
    • H01L51/0034Organic polymers or oligomers
    • H01L51/0035Organic polymers or oligomers comprising aromatic, heteroaromatic, or arrylic chains, e.g. polyaniline, polyphenylene, polyphenylene vinylene
    • H01L51/0036Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H01L51/0037Polyethylene dioxythiophene [PEDOT] and derivatives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/08Polysulfonates
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/54Material technologies
    • Y02E10/549Material technologies organic PV cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/13Ultracapacitors, supercapacitors, double-layer capacitors
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31533Of polythioether

Description

    FIELD OF THE INVENTION
  • The invention relates to aqueous dispersions of electrically conducting polymers of thiophene, wherein the electrically conducting polymer is synthesized in the presence of polymeric acid colloids.
  • BACKGROUND OF THE INVENTION
  • Electrically conducting polymers have been used in a variety of organic electronic devices, including in the development of electroluminescent ("EL") devices for use in light emissive displays. With respect to EL devices, such as organic light emitting diodes (OLEDs) containing conducting polymers, such devices generally have the following configuration:
    • anode/buffer layer/EL material/cathode
  • The anode is typically any material that is transparent and has the ability to inject holes into the EL material, such as, for example, indium/tin oxide (ITO). The anode is optionally supported on a glass or plastic substrate. EL materials include fluorescent dyes, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof. The cathode is typically any material (such as, e.g., Ca or Ba) that has the ability to inject electrons into the EL material.
  • The buffer layer is typically an electrically conducting polymer and facilitates the injection of holes from the anode into the EL material layer. The buffer layer can also be called a hole-injection layer, a hole transport layer, or may be characterized as part of a bilayer anode. Typical conducting polymers employed as buffer layers include polyaniline and polydioxythiophenes such as poly(3,4-ethylenedioxythiophene) (PEDT). These materials can be prepared by polymerizing aniline or dioxythiophene monomers in aqueous solution in the presence of a water soluble polymeric acid, such as poly(styrenesulfonic acid) (PSS), as described in, for example, U.S. Patent No. 5,300,575 entitled "Polythiophene dispersions, their production and their use." A well known PEDT/PSS material is Baytron®-P, commercially available from H. C. Starck, GmbH (Leverkusen, Germany).
  • The aqueous electrically conductive polymer dispersions synthesized with water soluble polymeric sulfonic acids have undesirable low pH levels. The low pH can contribute to decreased stress life of an EL device containing such a buffer layer, and contribute to corrosion within the device. Accordingly, there is a need for compositions and layers prepared there from having improved properties.
  • Electrically conducting polymers which have the ability to carry a high current when subjected to a low electrical voltage, also have utility as electrodes for electronic devices, such as thin film field effect transistors. In such transistors, an organic semiconducting film which has high mobility for electron and/or hole charge carriers, is present between source and drain electrodes. A gate electrode is on the opposite side of the emiconducting polymer layer. To be useful for the electrode application, the electrically conducting polymers and the liquids for dispersing or dissolving the electrically conducting polymers have to be compatible with the semiconducting polymers and the solvents for the semiconducting polymers to avoid re-dissolution of either conducting polymers or semiconducting polymers. The electrical conductivity of the electrodes fabricated from the electrically conducting polymers should be greater than 10 S/cm (where S is a reciprocal ohm). However, the electrically conducting polythiophenes made with a polymeric acid typically provide conductivity in the range of ∼10-3 S/cm or lower. In order to enhance conductivity, conductive additives may be added to the polymer. However, the presence of such additives can deleteriously affect the processability of the electrically conducting polythiophene. Accordingly, there is a need for improved conductive polythiophenes.
  • SUMMARY OF THE INVENTION
  • Compositions are described herein comprising aqueous dispersions of at least one polythiophene and at least one colloid-forming polymeric acid, wherein the polythiophene comprises the Formula I(a) or I(b): wherein
    with respect to Formula I(a):
    Figure imgb0001
  • R"
    is the same or different at each occurrence and is selected from hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, and urethane, with the proviso that at least one R" is not hydrogen.
    m
    is 2 or 3, and
    n
    is at least 4;
    and, with respect to Formula I(b):
    Figure imgb0002
    R'1 and R1
    are independently selected from hydrogen or alkyl, or
    R'1 and R1
    taken together form an alkylene chain having 1 to 4 carbon atoms, which may optionally be substituted by alkyl or aromatic groups having 1 to 12 carbon atoms, or a 1,2- cyclohexylene radical, and
    n
    is at least 4.
  • The invention provides a method according to claim 1. One method of producing an aqueous dispersion of the polythiophene and at least one colloid-forming polymeric acid, comprises:
  1. 1. (a) providing a homogeneous aqueous mixture of water and at least one thiophene monomer, said thiophene having Formula II(a) or II(b):
    Figure imgb0003
    wherein R", R'1, and R1 and m are as defined above;
  2. 2. (b) providing an aqueous dispersion of the colloid-forming polymeric acid;
  3. 3. (c) combining the thiophene mixture with the aqueous dispersion of the colloid-forming polymeric acid, and
  4. 4. (d) combining an oxidizing agent and a catalyst, in any order, with the aqueous dispersion of the colloid-forming polymeric acid before or after the combining of step (c).
  • In another embodiment, compositions are described herein comprising at least one polythiophene, at least one colloid-forming polymeric acid, and at least one co-dispersing liquid, wherein the polythiophene comprises the Formula I(a) or I(b), as described above.
  • In another embodiment, electronic devices comprising at least one layer comprising the composition are described.
  • The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims.
  • BRIEF DESCRIPTION OF THE FIGURES
  • The invention is illustrated by way of example and not limited in the accompanying figures.
    • FIG. 1 illustrates a cross-sectional view of an electronic device that comprises a buffer layer comprising one embodiment of the composition described herein.
    • FIG. 2 illustrates a cross-sectional view of a thin film field effect transistor that comprises an electrode comprising the composition described herein.
    • FIG. 3 illustrates the change in conductivity of polythiophene/FSA aqueous colloidal dispersion® films with the ratio of oxidizing agent to monomer in the polymerization reaction.
    • FIG. 4 illustrates the change in conductivity of polythiophene/FSA aqueous colloidal dispersion films with the ratio of FSA to monomer in the polymerization reaction.
    • FIG. 5 illustrates the operation lifetime of OLED devices with green light-emitting polymers.
    • FIG. 6 illustrates the operation lifetime of OLED devices with red light-emitting polymers.
    • FIG. 7 illustrates the operation lifetime of OLED devices with blue light-emitting polymers.
    • FIG. 8(a) through FIG. 8(d) illustrate the effect of the pH of the PEDT/PSSA buffer layer on OLED device performance.
    • FIG. 9(a) through FIG. 9(c) illustrate the effect of the pH of the polythiophene/FSA aqueous colloidal dispersion buffer layer on OLED device performance.
    • FIG. 10 illustrates the change in ITO thickness when immersed in dispersions of polythiophene/FSA aqueous colloidal dispersion or PEDT/PSSA.
    • FIG. 11 illustrates a device luminance and voltage as a function of time.
    DETAILED DESCRIPTION OF THE INVENTION
  • In one embodiment, compositions are described herein comprising aqueous dispersions of at least one polythiophenes having Formula I(a) or Formula I(b), and at least one colloid-forming polymeric acid.
  • The aqueous dispersion of at least one polythiophene and at least one colloid-forming polymeric acid comprising at least one polythiophene having Formula I(a) or Formula I(b) can be prepared when at least one thiophene monomer having Formula 11(a) or II(b) are polymerized chemically in the presence of colloid-forming polymeric acids.
  • Further, it has been discovered that use of a polymeric acid that is not water soluble in preparation of an aqueous dispersion of the polythiophenes having Formula II(a) or Formula II(b) yields a composition with superior electrical properties. In one embodiment, the aqueous dispersions of the composition comprises electrically conductive minute particles that are stable in the aqueous medium without forming a separate phase over a long period of time before a use. In one embodiment, layers comprising the composition do not re-disperse once dried into films or layers during fabrication of the electronic device.
  • Compositions according to one embodiment of the composition described herein comprise a continuous aqueous phase in which at least one polythiophene and at least one colloid-forming polymeric acid are dispersed.
  • Polythiophenes contemplated for use in the invention are made from at least one monomer having the following Formulae II(a) or II(b) to create either homopolymers or copolymers, wherein:
    Figure imgb0004
  • R"
    is the same or different at each occurrence and is selected from hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, sulfonate, and urethane, with the proviso that at least one R" is not hydrogen;
    m
    is 2 or 3;
    R'1, and R1
    are independently selected from hydrogen or alkyl, or
    R1 and R1'
    taken together form an alkylene chain having 1 to 4 carbon atoms, which may optionally be substituted by alkyl or aromatic groups having 1 to 12 carbon atoms, or a 1,2- cyclohexylene radical.
  • Thiophenes of the composition have the same general structure as provided above, wherein R1 and R1' are substituted for the "OR1" and "OR1'" substituents.
  • The polythiophenes of the composition can be homopolymers, or they can be copolymers of two or more thiophene monomers. The aqueous dispersions of polythiophene and colloid-forming polymeric acid can comprise one or more than one polythiophene polymer and one or more than one colloid-forming polymeric acid.
  • As used herein, the term "dispersion" refers to a continuous liquid medium containing a suspension of minute particles. The "continuous medium" comprises an aqueous liquid. As used herein, the term "aqueous" refers to a liquid that has a significant portion of water and in one embodiment it is at least about 40% by weight water. As used herein, the term "colloid" refers to the minute particles suspended in the continuous medium, said particles having a nanometer-scale particle size. As used herein, the term "colloid-forming" refers to substances that form minute particles when dispersed in aqueous solution, i.e., "colloid-forming" polymeric acids are not water-soluble.
  • As used herein, the term "co-dispersing liquid" refers to a substance which is liquid at room temperature and is miscible with water. As used herein, the term "miscible" means that the co-dispersing liquid is capable of being mixed with water (at concentrations set forth herein for each particular co-dispersing liquid) to form a substantially homogeneous solution.
  • The term "layer" or "film" refers to a coating covering a desired area. The area can be as large as an entire device or as small as a specific functional area such as the actual visual display, or as small as a single sub-pixel. Films can be formed by any conventional deposition technique, including vapor deposition and liquid deposition. Typical liquid deposition techniques include, but are not limited to, continuous deposition techniques such as spin coating, gravure coating, curtain coating, dip coating, slot-die coating, spray coating, and continuous nozzle coating; and discontinuous deposition techniques such as ink jet printing, gravure printing, and screen printing.
  • As used herein, the term "alkyl" refers to a group derived from an aliphatic hydrocarbon and includes linear, branched and cyclic groups which may be unsubstituted or substituted. The term "heteroalkyl" is intended to mean an alkyl group, wherein one or more of the carbon atoms within the alkyl group has been replaced by another atom, such as nitrogen, oxygen, sulfur, and the like. The term "alkylene" refers to an alkyl group having two points of attachment.
  • As used herein, the term "alkenyl" refers to a group derived from an aliphatic hydrocarbon having at least one carbon-carbon double bond, and includes linear, branched and cyclic groups which may be unsubstituted or substituted. The term "heteroalkenyl" is intended to mean an alkenyl group, wherein one or more of the carbon atoms within the alkenyl group has been replaced by another atom, such as nitrogen, oxygen, sulfur, and the like. The term "alkenylene" refers to an alkenyl group having two points of attachment.
  • As used herein, the following terms for substituent groups refer to the formulae given below:
    "alcohol" -R3-OH
    amidosulfonate -R3-C(O)N(R6)R4-SO3Z
    "benzyl" CH2-C6H5
    "carboxylate" -R3-C(O)O-Z
    "ether" -R3-O-R5
    "ether carboxylate" -R3-O-R4-C(O)O-Z
    "ether sulfonate" -R3-O-R4-SO3Z
    "sulfonate" -R3-SO3Z
    "urethane" -R3-O-C(O)-N(R6)2
    where all "R" groups are the same or different at each occurrence and:
    • R3 is a single bond or an alkylene group
    • R4 is an alkylene group
    • R5 is an alkyl group
    • R6 is hydrogen or an alkyl group
    • Z is H, alkali metal, alkaline earth metal, N(R5)4 or R5.
  • Any of the above groups may further be unsubstituted or substituted, and any group may have F substituted for one or more hydrogens, including perfluorinated groups.
  • In one embodiment, the polythiophene has Formula I(a) where m is two, one R" is an alkyl group of more than 5 carbon atoms, and all other R" are hydrogen.
  • In one embodiment of Formula I(a), at least one R" group has at least one fluorine substituent.
  • In one embodiment of Formula I(a), the R" substituents on the fused alicyclic ring on the thiophene should offer improved solubility of the monomers in water and facilitate polymerization in the presence of the polymeric acid colloids. In another embodiment, the resulting polythiophene/colloidal polymeric acid composition has reduced particle size and dispersion stability.
  • In one embodiment, the polythiophene is a poly[(sulfonic acid-propylene-ether-methylene-3,4-dioxyethylene)thiophene]. In one embodiment, the polythiophene is a poly[(propyl-ether-ethylene-3,4-dioxyethylene)thiophene].
  • In one embodiment, the polythiophene has Formula I(b) where R1 and R1' taken together form an alkylene chain having 1 to 4 carbon atoms. In another embodiment, the polydioxythiophene is poly(3,4-ethylenedioxythiophene).
  • Colloid-forming polymeric acids contemplated for use in the invention are insoluble in water, and form colloids when dispersed into an aqueous medium. The polymeric acids typically have a molecular weight in the range of 10,000 to 4,000,000.
  • In one embodiment, the polymeric acids have a molecular weight of 100,000 to 2,000,000. Polymeric acid colloid particle size typically ranges from 2 nanometers (nm) to 140 nm. In one embodiment, the colloids have a particle size of 2 nm to 30 nm.
  • Any polymeric acid that is colloid-forming when dispersed in water is suitable for use to make the compositions described herein. In the methods of the invention, the colloid-forming polymeric acid comprises a fluorinated polymeric sulfonic acid and optionally at least one polymeric acid selected from polymeric phosphoric acids, polymeric phosphonic acids, polymeric carboxylic acids, and polymeric acrylic acids, and mixtures thereof. In another embodiment, the colloid-forming polymeric sulfonic acid is perfluorinated. In yet another embodiment, the colloid-forming polymeric sulfonic acid comprises a perfluoroalkylenesulfonic acid.
  • In still another embodiment, the colloid-forming polymeric acid comprises a highly-fluorinated sulfonic acid polymer ("FSA polymer"). "Highly fluorinated" means that at least about 50% of the total number of halogen and hydrogen atoms in the polymer are fluorine atoms, an in one embodiment at least about 75%, and in another embodiment at least about 90%. In one embodiment, the polymer is perfluorinated. The term "sulfonate functional group" refers to either to sulfonic acid groups or salts of sulfonic acid groups, and in one embodiment alkali metal or ammonium salts. The functional group is represented by the formula -SO3X where X is a cation, also known as a "counterion". X may be H, Li, Na, K or N(R1)(R2)(R3)(R4), and R1, R2, R3, and R4 are the same or different and are and in one embodiment H, CH3 or C2H5. In another embodiment, X is H, in which case the polymer is said to be in the "acid form". X may also be multivalent, as represented by such ions as Ca++, and Al+++. It is clear to the skilled artisan that in the case of multivalent counterions, represented generally as Mn+, the number of sulfonate functional groups per counterion will be equal to the valence "n".
  • In one embodiment, the FSA polymer comprises a polymer backbone with recurring side chains attached to the backbone, the side chains carrying cation exchange groups. Polymers include homopolymers or copolymers of two or more monomers. Copolymers are typically formed from a nonfunctional monomer and a second monomer carrying the cation exchange group or its precursor, e.g., a sulfonyl fluoride group (-SO2F), which can be subsequently hydrolyzed to a sulfonate functional group. For example, copolymers of a first fluorinated vinyl monomer together with a second fluorinated vinyl monomer having a sulfonyl fluoride group (-SO2F) can be used. Possible first monomers include tetrafluoroethylene (TFE), hexafluoropropylene, vinyl fluoride, vinylidine fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoro(alkyl vinyl ether), and combinations thereof. TFE is a preferred first monomer.
  • In other embodiments, one other monomer includes fluorinated vinyl ethers with sulfonate functional groups or precursor groups which can provide the desired side chain in the polymer. Additional monomers, including ethylene, propylene, and R-CH=CH2 where R is a perfluorinated alkyl group of 1 to 10 carbon atoms, can be incorporated into these polymers if desired. The polymers may be of the type referred to herein as random copolymers, that is copolymers made by polymerization in which the relative concentrations of the co-monomers are kept as constant as possible, so that the distribution of the monomer units along the polymer chain is in accordance with their relative concentrations and relative reactivities. Less random copolymers, made by varying relative concentrations of monomers in the course of the polymerization, may also be used. Polymers of the type called block copolymers, such as that disclosed in European Patent Application No. 1 026 152 A1 , may also be used.
  • In one embodiment, FSA polymers for use in the invention include a highly fluorinated, and in one embodiment perfluorinated, carbon backbone and side chains represented by the formula

            -(O-CF2CFRf)a-O-CF2CFR'fSO3X

    wherein Rf and R'f are independently selected from F, Cl or a perfluorinated alkyl group having 1 to 10 carbon atoms, a = 0, 1 or 2, and X is H, Li, Na, K or N(R1)(R2)(R3)(R4) and R1, R2, R3, and R4 are the same or different and are and in one embodiment H, CH3 or C2H5. In another embodiment X is H. As stated above, X may also be multivalent.
  • In one embodiment, the FSA polymers include, for example, polymers disclosed in U.S. Patent No. 3,282,875 and in U.S. Patent Nos. 4,358,545 and 4,940,525 . An example of preferred FSA polymer comprises a perfluorocarbon backbone and the side chain represented by the formula

            -O-CF2CF(CF3)-O-CF2CF2SO3X

    where X is as defined above. FSA polymers of this type are disclosed in U.S. Patent No. 3,282,875 and can be made by copolymerization of tetrafluoroethylene (TFE) and the perfluorinated vinyl ether CF2=CF-O-CF2CF(CF3)-O-CF2CF2SO2F, perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) (PDMOF), followed by conversion to sulfonate groups by hydrolysis of the sulfonyl fluoride groups and ion exchanged as necessary to convert them to the desired ionic form. An example of a polymer of the type disclosed in U.S. Patent Nos. 4,358,545 and 4,940,525 has the side chain -O-CF2CF2SO3X, wherein X is as defined above. This polymer can be made by copolymerization of tetrafluoroethylene (TFE) and the perfluorinated vinyl ether CF2=CF-O-CF2CF2SO2F, perfluoro(3-oxa-4-pentenesulfonyl fluoride) (POPF), followed by hydrolysis and further ion exchange as necessary.
  • In one embodiment, the FSA polymers for use in the invention typically have an ion exchange ratio of less than about 33. In this application, "ion exchange ratio" or "IXR" is defined as number of carbon atoms in the polymer backbone in relation to the cation exchange groups. Within the range of less than about 33, IXR can be varied as desired for the particular application. In one embodiment, the IXR is 3 to 33, and in another embodiment 8 to 23.
  • The cation exchange capacity of a polymer is often expressed in terms of equivalent weight (EW). For the purposes of this application, equivalent weight (EW) is defined to be the weight of the polymer in acid form required to neutralize one equivalent of sodium hydroxide. In the case of a sulfonate polymer where the polymer has a perfluorocarbon backbone and the side chain is -O-CF2-CF(CF3)-O-CF2-CF2-SO3H (or a salt thereof), the equivalent weight range which corresponds to an IXR of 8 to 23 is about 750 EW to about 1500 EW. IXR for this polymer can be related to equivalent weight using the formula: 50 IXR + 344 = EW. While the same IXR range is used for sulfonate polymers disclosed in U.S. Patent Nos. 4,358,545 and 4,940,525 , e.g., the polymer having the side chain -O-CF2CF2SO3H (or a salt thereof), the equivalent weight is somewhat lower because of the lower molecular weight of the monomer unit containing a cation exchange group. For the preferred IXR range of 8 to 23, the corresponding equivalent weight range is 575 EW to 1325 EW. IXR for this polymer can be related to equivalent weight using the formula: 50 IXR + 178 = EW.
  • The synthesis of FSA polymers is well known. The FSA polymers can be prepared as colloidal aqueous dispersions. They may also be in the form of dispersions in other media, examples of which include, but are not limited to, alcohol, water-soluble ethers, such as tetrahydrofuran, mixtures of water-soluble ethers, and combinations thereof. In making the dispersions, the polymer can be used in acid form. U.S. Patent Nos. 4,433,082 , 6,150,426 and WO 03/006537 disclose methods for making of aqueous dispersions. After the dispersion is made, the concentration and the dispersing liquid composition can be adjusted by methods known in the art.
  • In one embodiment, aqueous dispersions of the colloid-forming polymeric acids, including FSA polymers, have particle sizes as small as possible and an EW as small as possible, so long as a stable colloid is formed.
  • Aqueous dispersions of FSA polymer are available commercially as Nafion® dispersions, from E.I. du Pont de Nemours and Company (Wilmington, DE).
  • The thiophene monomers having Formula II(a) or Formula II(b) are oxidatively polymerized in water comprising at least one polymeric acid colloids. The thiophene monomers are combined with or added to an aqueous dispersion containing a polymerization catalyst, an oxidizing agent, and colloidal polymeric acid particles dispersed therein. The order of combination or addition may vary provided that when the oxidizing agent and catalyst is combined with the monomers at least a portion of the colloid-forming polymeric acid is present. In one embodiment, the reaction mixture may further comprise a a co-acid.
  • In one embodiment, the colloid-forming polymeric acid is an FSA, and co-dispersing liquid of the aqueous FSA dispersion is removed prior to polymerization of thiophene monomers.
  • In one embodiment, the thiophene monomers are combined with the aqueous reaction mixture comprising colloid-forming polymeric acid particles, the oxidizing agent and the catalyst by dispensing the thiophene monomer in a controlled rate of addition while continuously mixing the reaction mixture to form a monomer-meniscus in the reaction mixture.
  • In one embodiment, the oxidizing agent predissolved in water is combined with the aqueous reaction mixture comprising colloid-forming polymeric acid particles, thiophene monomer and the catalyst therein by dispensing the oxidizing agent solution in a controlled rate of addition while continuously mixing the reaction mixture.
  • In one embodiment, the oxidizing agent and the thiophene monomer are added separately and simultaneously to the reaction mixture, at the same or different controlled rates of addition, to achieve the final desired quantity of oxidizing agent, so as to consume the monomer at a controlled rate in the oxidative polymerization reaction.
  • In one embodiment, the controlled rate of addition of thiophene monomer is determined in view of the quantity of materials used, with the goal of controlling the rate of monomer addition from the dispensing mechanism to ensure dissolution in the reaction mixture quickly. With the controlled addition, the polymerization and oxidation chemistry take place in an even and uniform manner. Examples of the dispensing mechanism include, but are not limited to, use of tubing, syringes, pipettes, nozzle guns, sprayers, hoses, pipes and the like. In one embodiment, a perforated end, such as a fritted-glass plate, or small diameter tubing attached to the equipment described above is used for creating a monomer-meniscus in the reaction mixture.
  • The rate of addition depends upon the size of the reaction, the speed at which the solution is stirred and the geometry and number of the dispensing ends of the dispensing mechanism orifice. In one embodiment, the dispensing end of the dispensing mechanism is submerged in the reaction mixture containing the aqueous colloid-forming polymeric acid. For example, addition rates of thiophene monomer of 1-1000 micro liter per hour for a reaction mixture size of 100-500 grams of aqueous colloid-forming polymeric acid composition can be used. In one embodiment the rate of addition is between 5 and 100 micro liters per hour for 500 grams of the aqueous colloid-forming polymeric acid. For reaction mixtures of other sizes (larger or smaller), the rate of addition can be linearly scaled in the appropriate direction.
  • At least one co-dispersing liquid is added to the reaction mixture after the termination of the polymerization of the thiophene.
  • Polymerization catalysts include, but are not limited to, ferric sulfate, ferric chloride, other materials having a higher oxidation potential than the oxidizing agent, and mixtures thereof.
  • Oxidizing agents include, but are not limited to, sodium persulfate, potassium persulfate, ammonium persulfate, and the like, including combinations thereof. In one embodiment, the oxidative polymerization results in a stable, aqueous dispersion containing positively charged conductive polymeric thiophene that is charge balanced by the negatively charged side chains of the polymeric acids contained within the colloids, for example, sulfonate anion, carboxylate anion, acetylate anion, phosphorate anion, phosphonate anion, combinations, and the like.
  • In one embodiment, the method of making the composition comprising at least one polythiophene having Formula I(a) or Formula I(b) and at least one colloid-forming polymer acid includes: (a) providing an aqueous dispersion of a polymer acid; (b) adding an oxidizing agent to the dispersion of step (a); (c) adding a catalyst to the dispersion of step (b); and (d) adding a thiophene monomer to the dispersion of step (c). One alternative embodiment to the above described method includes adding the thiophene monomer to the aqueous dispersion of a polymeric acid prior to adding the oxidizing agent. Another embodiment is to create a homogenous aqueous mixture of water and the thiophene having Formula II(a) or Formula II(b), with concentrations which typically are in the range of 0.5% by weight to 2.0% by weight thiophene, and add this thiophene mixture to the aqueous dispersion of the polymeric acid before adding the oxidizing agent and catalyst.
  • Examples of suitable co-dispersing liquids include, but are not limited to ethers, alcohols, alcohol ethers, cyclic ethers, ketones, nitriles, sulfoxides, and combinations thereof. In one embodiment, the amount of co-dispersing liquid should be less than 30% by volume. In one embodiment, the amount of co-dispersing liquid is less than 60% by volume. In one embodiment, the amount of co-dispersing liquid is between 5% to 50% by volume. In one embodiment, the co-dispersing liquid comprises an alcohol. In one embodiment, the co-dispersing liquid comprises at least one from n-propanol, isopropanol, t-butanol, methanol dimethylacetamide, dimethylformamide, N-methylpyrrolidone.
  • The polymerization can be carried out in the presence of a co-acid. The acid can be an inorganic acid, such as HCl, sulfuric acid, and the like, or an organic acid, such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, acetic acid and the like. Alternatively, the co-acid can be a water soluble polymeric acid such as poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1-propanesulfonic acid, or the like, or a second colloid-forming acid, as described above. Combinations of co-acids can be used.
  • The co-acid can be added to the reaction mixture at any point in the process prior to the addition of either the oxidizing agent or the thiophene monomer, whichever is added last. In one embodiment, the co-acid is added before both the thiophene monomer and the colloid-forming polymeric acid, and the oxidizing agent is added last. In one embodiment the co-acid is added prior to the addition of the thiophene monomer, followed by the addition of the colloid-forming polymeric acid, and the oxidizing agent is added last.
  • The co-dispersing liquid is added to the reaction mixture at any point after the thiophene polymerization.
  • In one embodiment, compositions are described herein comprising aqueous dispersions of polydioxythiophenes, colloid-forming polymeric acids, and at least one co-dispersing liquid. The addition of at least one co-dispersing liquid to aqueous dispersions of poly(dioxythiophenes) and colloid-forming polymeric acids after polymerization can result in polymer dispersions having better wettability, and processability, processable viscosity, a substantially reduced number of large particles, improved stability of the dispersion, improved ink-jetability, enhanced conductivity, or combinations thereof. Surprisingly, it has been discovered that OLED devices having buffer layers made from such dispersions also have higher efficiencies and longer lifetimes.
  • Co-dispersing liquids contemplated for use in the invention are generally polar, water-miscible organic liquids. Examples of suitable types of co-dispersing liquids include, but are not limited to, ethers, cyclic ethers, alcohols, alcohol ethers, ketones, nitriles, sulfides, sulfoxides, amides, amines, carboxylic acids, and the like, as well as combinations of any two or more thereof.
  • Exemplary ether co-dispersing liquids contemplated for use in the invention include, but are not limited to, diethyl ether, ethyl propyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl t-butyl ether, glyme, diglyme, benzyl methyl ether, isochroman, 2-phenylethyl methyl ether, n-butyl ethyl ether, 1,2-diethoxyethane, sec-butyl ether, diisobutyl ether, ethyl n-propyl ether, ethyl isopropyl ether, n-hexyl methyl ether, n-butyl methyl ether, methyl n-propyl ether, and the like, as well as combinations of any two or more thereof.
  • Exemplary cyclic ether co-dispersing liquids contemplated for use in the invention include, but are not limited to, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, 4 methyl-1,3-dioxane, 4-phenyl-1,3-dioxane, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 1,3-dioxane, 2,5-dimethoxytetrahydrofuran, 2,5-dimethoxy-2,5-dihydrofuran, and the like, as well as combinations of any two or more thereof. In one embodiment, the cyclic ether co-dispersing liquid is tetrahydrofuran, tetrahydropyran, or 1,4-dioxane.
  • Exemplary alcohol co-dispersing liquids contemplated for use in the invention include, but are not limited to, methanol, ethanol, 1-propanol, 2-propanol (i.e., isopropanol), 1-butanol, 2-butanol, 2-methyl-1-propanol (i.e., isobutanol), 2-methyl-2-propanol (i.e., tert-butanol), 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 1-hexanol, cyclopentanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-hexanol, 2-hexanol, 4-methyl-2-pentanol, 2-methyl-1-pentanol, 2-ethylbutanol, 2,4-dimethyl-3-pentanol, 3-heptanol, 4-heptanol, 2-heptanol, 1-heptanol, 2-ethyl-1-hexanol, 2,6-dimethyl-4-heptanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, and the like, as well as combinations of any two or more thereof. In one embodiment, the alcohol co-dispersing liquid is methanol, ethanol, or isopropanol.
  • Exemplary alcohol ether co-dispersing liquids contemplated for use in the invention include, but are not limited to, 2-butoxyethanol, 1-methoxy-2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-butanol, ethylene glycol monoisopropyl ether, 1-ethoxy-2-propanol, 3-methoxy-1-butanol, ethylene glycol monoisobutyl ether, ethylene glycol mono-n-butyl ether, 3-methoxy-3-methylbutanol, ethylene glycol mono-tert-butyl ether, and the like, as well as combinations of any two or more thereof. In one embodiment, the alcohol ether co-dispersing liquid is 1-methoxy-2-propanol, 2-methoxyethanol, or 2-butoxyethanol.
  • Exemplary ketone co-dispersing liquids contemplated for use in the invention include, but are not limited to, acetone, methylethyl ketone, methyl iso-butyl ketone, cyclohexanone, isopropyl methyl ketone, 2-pentanone, 3-pentanone, 3-hexanone, diisopropyl ketone, 2-hexanone, cyclopentanone, 4-heptanone, iso-amyl methyl ketone, 3-heptanone, 2-heptanone, 4-methoxy-4-methyl-2-pentanone, 5-methyl-3-heptanone, 2-methylcyclohexanone, diisobutyl ketone, 5-methyl-2-octanone, 3-methylcyclohexanone, 2-cyclohexen-1-one, 4-methylcyclohexanone, cycloheptanone, 4-tert-butylcyclohexanone, isophorone, benzyl acetone, and the like, as well as combinations of any two or more thereof.
  • Exemplary nitrile co-dispersing liquids contemplated for use in the invention include, but are not limited to, acetonitrile, acrylonitrile, trichloroacetonitrile, propionitrile, pivalonitrile, isobutyronitrile, n-butyronitrile, methoxyacetonitrile, 2-methylbutyronitrile, isovaleronitrile, n-valeronitrile, n-capronitrile, 3-methoxypropionitrile, 3-ethoxypropionitrile, 3,3'-oxydipropionitrile, n-heptanenitrile, glycolonitrile, benzonitrile, ethylene cyanohydrin, succinonitrile, acetone cyanohydrin, 3-n-butoxypropionitrile, and the like, as well as combinations of any two or more thereof.
  • Exemplary sulfoxide co-dispersing liquids contemplated for use in the invention include, but are not limited to, dimethyl sulfoxide (DMSO), di-n-butyl sulfoxide, tetramethylene sulfoxide, methyl phenyl sulfoxide, and the like, as well as combinations of any two or more thereof.
  • Exemplary amide co-dispersing liquids contemplated for use in the invention include, but are not limited to, dimethyl formamide (DMF), dimethyl acetamide, acylamide, 2-acetamidoethanol, N,N-dimethyl-m-toluamide, trifluoroacetamide, N,N-dimethylacetamide, N,N-diethyldodecanamide, ε-caprotactam, N,N-diethylacetamide, N-tert-butylformamide, formamide, pivalamide, N-butyramide, N,N-dimethylacetoacetamide, N-methyl formamide, N,N-diethylformamide, N-formylethylamine, acetamide, N,N-diisopropylformamide, 1-formylpiperidine, N-methylformanilide, and the like, as well as combinations of any two or more thereof.
  • Exemplary amine co-dispersing liquids contemplated for use in the invention include, but are not limited to, mono-, di-, and tri-alkyl amines, cyclic amines (such as, e.g., pyrrolidine), aromatic amines (such as, e.g., pyridine) and the like, as well as combinations of any two or more thereof. In one embodiment, the amine co-dispersing liquid is pyridine.
  • Exemplary carboxylic acid co-dispersing liquids contemplated for use in the invention include, but are not limited to, C1 up to about C6 straight or branched chain carboxylic acids, as well as combinations of any two or more thereof. In one embodiment, the carboxylic acid co-dispersing liquid is formic acid.
  • In one embodiment, the co-dispersing liquid comprises a liquid selected from, n-propanol, isopropanol, methanol, butanol, 1-methoxy-2-propanol, dimethylacetamide, n-methyl pryrozole, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, 4 methyl-1,3-dioxane, 4-phenyl-1,3-dioxane, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 1,3-dioxane, 2,5-dimethoxytetrahydrofuran, 2,5-dimethoxy-2,5-dihydrofuran, 1-methylpyrrolindine, 1-methyl-2-pyrrolidinone, dimethylsulfoxide, and combinations of any two or more thereof.
  • In one embodiment, after completion of any of the methods described above and completion of the polymerization reaction, the as-synthesized aqueous dispersion is contacted with at least one ion exchange resin under conditions suitable to remove decomposed species, side reaction products, unreacted monomers, and ionic impurities, and to adjust pH. The as-synthesized aqueous dispersion can be contacted with at least one ion exchange resin before or after the addition of a co-dispersing liquid. In one embodiment, the as-synthesized aqueous dispersion is contacted with a first ion exchange resin and a second ion exchange resin.
  • In another embodiment, the first ion exchange resin is an acidic, cation exchange resin, such as a sulfonic acid cation exchange resin set forth above, and the second ion exchange resin is a basic, anion exchange resin, such as a tertiary amine or a quaternary exchange resin.
  • Ion exchange is a reversible chemical reaction wherein an ion in a fluid medium (such as an aqueous dispersion) is exchanged for a similarly charged ion attached to an immobile solid particle that is insoluble in the fluid medium. The term "ion exchange resin" is used herein to refer to all such substances. The resin is rendered insoluble due to the crosslinked nature of the polymeric support to which the ion exchanging groups are attached. Ion exchange resins are classified as acidic, cation exchangers, which have positively charged mobile ions available for exchange, and basic, anion exchangers, whose exchangeable ions are negatively charged.
  • Both acidic, cation exchange resins and basic, anion exchange resins are contemplated for use in the new process. In one embodiment, the acidic, cation exchange resin is an organic acid, cation exchange resin, such as a sulfonic acid cation exchange resin. Sulfonic acid cation exchange resins contemplated for use in the invention include, for example, sulfonated styrene-divinylbenzene copolymers, sulfonated crosslinked styrene polymers, phenol-formaldehyde-sulfonic acid resins, benzene-formaldehyde-sulfonic acid resins, and mixtures thereof. In another embodiment, the acidic, cation exchange resin is an organic acid, cation exchange resin, such as carboxylic acid, acrylic or phosphoric acid cation exchange resin. In addition, mixtures of different cation exchange resins can be used. In many cases, the basic ion exchange resin can be used to adjust the pH to the desired level. In some cases, the pH can be further adjusted with an aqueous basic solution such as a solution of sodium hydroxide, ammonium hydroxide,, or the like.
  • In another embodiment, the basic, anionic exchange resin is a tertiary amine anion exchange resin. Tertiary amine anion exchange resins contemplated for use in the invention include, for example, tertiary-aminated styrene-divinylbenzene copolymers, tertiary-aminated crosslinked styrene polymers, tertiary-aminated phenol-formaldehyde resins, tertiary-aminated benzene-formaldehyde resins, and mixtures thereof. In a further embodiment, the basic, anionic exchange resin is a quaternary amine anion exchange resin, or mixtures of these and other exchange resins.
  • The first and second ion exchange resins may contact the as-synthesized aqueous dispersion either simultaneously, or consecutively. For example, in one embodiment both resins are added simultaneously to an as-synthesized aqueous dispersion of an electrically conducting polymer, and allowed to remain in contact with the dispersion for at least 1 hour, e.g., 2 hours to 20 hours. The ion exchange resins can then be removed from the dispersion by filtration. The size of the filter is chosen so that the relatively large ion exchange resin particles will be removed while the smaller dispersion particles will pass through. Without wishing to be bound by theory, it is believed that the ion exchange resins quench polymerization and effectively remove ionic and non-ionic impurities and most of unreacted monomer from the as-synthesized aqueous dispersion. Moreover, the basic, anion exchange and/or acidic, cation exchange resins renders the acidic sites more basic, resulting in increased pH of the dispersion. In general, at least 1 gram of ion exchange is used per about 1 gram of colloid-forming polymeric acid. In other embodiments, the use of the ion exchange resin is used in a ratio of up to about 5 grams of ion exchange resin to polythiophene/polymeric acid colloid and depends on the pH that is to be achieved. In one embodiment, about one gram of Lewatit® MP62 WS, a weakly basic anion exchange resin from Bayer GmbH, and about one gram of Lewatit® MonoPlus S100, a strongly acidic, sodium cation exchange resin from Bayer, GmbH, are used per gram of the composition of polythiophene having Formula I(a) or Formula I(b) and at least one colloid-forming polymeric acid.
  • In one embodiment, the aqueous dispersion resulting from polymerization of thiophene having Formula II(a) or Formula II(b) with fluorinated polymeric sulfonic acid colloids is to charge a reaction vessel first with an aqueous dispersion of the fluorinated polymer, and then, in order, add the oxidizing agent, catalyst and thiophene monomer; or, in order, the thiophene monomer, the oxidizing agent and catalyst to the aqueous dispersion of the colloid-forming polymeric acid. The mixture is stirred and the reaction is then allowed to proceed at a controlled temperature. When polymerization is completed, the reaction is quenched with a strong acid cation resin and a base anion exchange resin, stirred and filtered. Alternatively, the thiophene having Formula II(a) or Formula II(b) can be added to water and stirred to homogenize the mixture prior to addition of Nation® dispersion, followed with oxidizing agent and catalyst. The oxidizing agent:monomer ratio is generally in the range of 0.5 to 2.0. The fluorinated polymer:thiophene monomer ratio is generally in the range of 1 to 4. The overall solid content is generally in the range of 1.5% to 6%; and in one embodiment 2% to 4.5%. The reaction temperature is generally in the range of 5°C to 50°C; and in one embodiment 20°C to 35°C. The reaction time is generally in the range of 1 to 30 hours.
  • Aqueous dispersions of polythiophenes of Formula I(a) or Formula I(b) and polymer acid colloids can have a wide range of pH and can be adjusted to typically be between 1 to 8, and generally have a pH of 3-4. It is frequently desirable to have a higher pH, as the acidity can be corrosive. In the methods of the invention the aqueous dispersion has a pH of 4 to 8. It has been found that the pH can be adjusted using known techniques, for example, ion exchange or by titration with an aqueous basic solution.
  • In another embodiment, more conductive dispersions are formed by the addition of highly conductive additives to the aqueous dispersions of polythiophene having Formula I(a) or Formula I(b) and the colloid-forming polymeric acid. In one embodiment, compositions with relatively high pH can be formed, and further comprise the conductive additives, especially metal additives, which are not attacked by the acid in the dispersion. Moreover, because the polymeric acids are colloidal in nature, having the surfaces predominately containing acid groups, electrically conducting polythiophene is formed on the colloidal surfaces.
  • In one embodiment, the composition further comprises at least one conductive additive at a weight percentage of an amount to reach the percolation threshold. Examples of suitable conductive additives include, but are not limited to conductive polymers, metal particles and nanoparticles, metal nanowires, carbon nanotubes, carbon nanopoarticles, graphite fibers or particles, carbon particles, and combinations thereof. A dispersing agent may be included to faciltate dispersing of the conductive additives.
  • In one embodiment, the compositions are deposited to form electrically conductive or semiconductive layers which are used alone, or in combination with other electroactive materials, as electrodes, electroactive elements, photoactive elements, or bioactive elements. As used herein, the terms "electroactive element", "photoactive element" and "bioactive element" refer to elements which exhibit the named activity in response to a stimulus, such as an electromagnetic field, an electrical potential, solar energy radiation, and a biostimulation field.
  • In one embodiment, the compositions are deposited to form buffer layers in an electronic device. The term "buffer layer" as used herein, is intended to mean an electrically conductive or semiconductive layer which can be used between an anode and an active organic material. A buffer layer is believed to accomplish one or more function in an organic electronic device, including, but not limited to planarization of the underlying layer, hole transport, hole injection, scavenging of impurities, such as oxygen and metal ions, among other aspects to facilitate or to improve the performance of an organic electronic device.
  • In one embodiment, described herein are buffer layers deposited from an aqueous dispersion containing polythiophene having Formula I(a) or Formula I(b) and fluorinated polymeric acid colloids. In another embodiment, the fluorinated polymeric acid colloids are fluorinated polymeric sulfonic acid colloids. In still another embodiment, the buffer layer is deposited from an aqueous dispersion containing polythiophene having Formula I(a) or Formula I(b) and perfluoroethylenesulfonic acid colloids.
  • In another embodiment, described herein are buffer layers deposited from aqueous dispersions comprising at least one polythiophene having Formula I(a) or Formula I(b), at least one colloid-forming polymeric acid, and at least one co-dispersing liquid. In one embodiment, the co-dispersing liquid is selected from n-propanol, isopropanol, t-butanol, methanol dimethylacetamide, dimethylformamide, N-methylpyrrolidone, ethylene glycol, and mixtures thereof.
  • In one embodiment, the dried layers of polythiophenes having Formula I(a) or Formula I(b) and polymeric acid colloids, such as fluorinated polymeric sulfonic acid colloids, are not redispersible in water. In one embodiment, the organic device comprising at least one layer comprising the composition is made of multiple thin layers. In one embodiment, the layer can be further overcoated with a layer of different water-soluble or water-dispersible material without substantial damage to the layer's functionality or performance in an organic electronic device.
  • In another embodiment, described herein are buffer layers deposited from aqueous dispersions comprising at least one polythiophene having Formula I(a) or Formula I(b) and at least one colloid-forming polymeric acids blended with other water soluble or dispersible materials. Depending on the final application of the material, examples of types of additional water soluble or dispersible materials which can be added include, but are not limited to polymers, dyes, coating aids, carbon nanotubes, metal nanowires and nanoparticles, organic and inorganic conductive inks and pastes, charge transport materials, piezoelectric, pyroelectric, or ferroelectric oxide nano-particles or polymers, photoconductive oxide nanoparticles or polymers, dispersing agents, crosslinking agents, and combinations thereof. The materials can be simple molecules or polymers. Examples of suitable other water soluble or dispersible polymers include, but are not limited to, polyacrylamide, polyvinylalcohol, poly(2-vinylpridine), poly(vinylacetate), poly(vinylmethylether), poly(vinylpyrrolidone), poly(vinylbutyral), poly(styrenesulfonic acid, and conductive polymers such as polythiophenes, polyanilines, polyamines, polypyrroles, polyacetylenes, colloid-forming polymeric acids, and combinations thereof.
  • In another embodiment, described herein are electronic devices comprising at least one electrically conductive or semiconductive layer made from the composition. Organic electronic devices that may benefit from having one or more layers comprising the composition of at least one polythiophene having Formula I(a) or Formula I(b), and at least one colloid-forming polymeric acids and include, but are not limited to, (1) devices that convert electrical energy into radiation (e.g., a light-emitting diode, light emitting diode display, or diode laser), (2) devices that detect signals through electronics processes (e.g., photodetectors (e.g., photoconductive cells, photoresistors, photoswitches, phototransistors, phototubes), IR detectors), (3) devices that convert radiation into electrical energy, (e.g., a photovoltaic device or solar cell), and (4) devices that include one or more electronic components that include one or more organic semi-conductor layers (e.g., a transistor or diode). Other uses for the compositions include coating materials for memory storage devices, antistatic films, biosensors, electrochromic devices, solid electrolyte capacitors, energy storage devices such as a rechargeable battery, and electromagnetic shielding applications.
  • In one embodiment, the organic electronic device comprises an electroactive layer positioned between two electrical contact layers, wherein at least one of the layers of the device includes the new buffer layer. One embodiment is illustrated in one type of OLED device, as shown in FIG. 1, which is a device that has anode layer 110, a buffer layer 120, an electroluminescent layer 130, and a cathode layer 150. Adjacent to the cathode layer 150 is an optional electron-injection/transport layer 140. Between the buffer layer 120 and the cathode layer 150 (or optional electron injection/transport layer 140) is the electroluminescent layer 130.
  • The device may include a support or substrate (not shown) that can be adjacent to the anode layer 110 or the cathode layer 150. Most frequently, the support is adjacent the anode layer 110. The support can be flexible or rigid, organic or inorganic. Generally, glass or flexible organic films are used as a support. The anode layer 110 is an electrode that is more efficient for injecting holes compared to the cathode layer 150. The anode can include materials containing a metal, mixed metal, alloy, metal oxide or mixed oxide. Suitable materials include the mixed oxides of the Group 2 elements (i.e., Be, Mg, Ca, Sr, Ba, Ra), the Group 11 elements, the elements in Groups 4, 5, and 6, and the Group 8-10 transition elements. If the anode layer 110 is to be light transmitting, mixed oxides of Groups 12, 13 and 14 elements, such as indium-tin-oxide, may be used. As used herein, the phrase "mixed oxide" refers to oxides having two or more different cations selected from the Group 2 elements or the Groups 12, 13, or 14 elements. Some non-limiting, specific examples of materials for anode layer 110 include, but are not limited to, indium-tin-oxide ("ITO"), aluminum-tin-oxide, gold, silver, copper, and nickel. The anode may also comprise an organic material such as polyaniline, polythiophene, or polypyrrole. The IUPAC number system is used throughout, where the groups from the Periodic Table are numbered from left to right as 1-18 (CRC Handbook of Chemistry and Physics, 81st Edition, 2000).
  • The anode layer 110 may be formed by a chemical or physical vapor deposition process or spin-coating process. Chemical vapor deposition may be performed as a plasma-enhanced chemical vapor deposition ("PECVD") or metal organic chemical vapor deposition ("MOCVD"). Physical vapor deposition can include all forms of sputtering, including ion beam sputtering, as well as e-beam evaporation and resistance evaporation. Specific forms of physical vapor deposition include rf magnetron sputtering and inductively-coupled plasma physical vapor deposition ("IMP-PVD"). These deposition techniques are well known within the semiconductor fabrication arts.
  • The anode layer 110 may be patterned during a lithographic operation. The pattern may vary as desired. The layers can be formed in a pattern by, for example, positioning a patterned mask or resist on the first flexible composite barrier structure prior to applying the first electrical contact layer material. Alternatively, the layers can be applied as an overall layer (also called blanket deposit) and subsequently patterned using, for example, a patterned resist layer and wet chemical or dry etching techniques. Other processes for patterning that are well known in the art can also be used. When the electronic devices are located within an array, the anode layer 110 typically is formed into substantially parallel strips having lengths that extend in substantially the same direction.
  • The buffer layer 120 can be deposited onto substrates using any techniques well-known to those skilled in the art.
  • The electroluminescent (EL) layer 130 may typically be any organic EL material, including, but not limited to, fluorescent dyes, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof. Examples of fluorescent dyes include, but are not limited to, pyrene, perylene, rubrene, derivatives thereof, and mixtures thereof. Examples of metal complexes include, but are not limited to, metal chelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq3); cyclometalated iridium and platinum electroluminescent compounds, such as complexes of Iridium with phenylpyridine, phenylquinoline, or phenylpyrimidine ligands as disclosed in Petrov et al., Published PCT Application WO 02/02714 , and organometallic complexes described in, for example, published applications US 2001/0019782 , EP 1191612 , WO 02/15645 , and EP 1191614 ; and mixtures thereof. Electroluminescent emissive layers comprising a charge carrying host material and a metal complex have been described by Thompson et al., in U.S. Patent 6,303,238 , and by Burrows and Thompson in published PCT applications WO 00/70655 and WO 01/41512 . Examples of conjugated polymers include, but are not limited to poly(phenylenevinylenes), polyfluorenes, poly(spirobifluorenes), polythiophenes, poly(p-phenylenes), copolymers thereof, and mixtures thereof.
  • The particular material chosen may depend on the specific application, potentials used during operation, or other factors. The EL layer 130 containing the electroluminescent organic material can be applied using any number of techniques including vapor deposition, solution processing techniques or thermal transfer. In another embodiment, an EL polymer precursor can be applied and then converted to the polymer, typically by heat or other source of external energy (e.g., visible light or UV radiation).
  • Optional layer 140 can function both to facilitate electron injection/transport, and can also serve as a confinement layer to prevent quenching reactions at layer interfaces. More specifically, layer 140 may promote electron mobility and reduce the likelihood of a quenching reaction if layers 130 and 150 would otherwise be in direct contact. Examples of materials for optional layer 140 include, but are not limited to, metal-chelated oxinoid compounds (e.g., Alq3); phenanthroline-based compounds (e.g., 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline ("DDPA"), 4,7-diphenyl-1,10-phenanthroline ("DPA"),); azole compounds (e.g., 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole ("PBD"), 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole ("TAZ"); other similar compounds; or any one or more combinations thereof. Alternatively, optional layer 140 may be inorganic and comprise BaO, LiF, Li2O,.
  • The cathode layer 150 is an electrode that is particularly efficient for injecting electrons or negative charge carriers. The cathode layer 150 can be any metal or nonmetal having a lower work function than the first electrical contact layer (in this case, the anode layer 110). As used herein, the term "lower work function" is intended to mean a material having a work function no greater than about 4.4 eV. As used herein, "higher work function" is intended to mean a material having a work function of at least approximately 4.4 eV.
  • Materials for the cathode layer can be selected from alkali metals of Group 1 (e.g., Li, Na, K, Rb, Cs,), the Group 2 metals (e.g., Mg, Ca, Ba,), the Group 12 metals, the lanthanides (e.g., Ce, Sm, Eu,), and the actinides (e.g., Th, U,). Materials such as aluminum, indium, yttrium, and combinations thereof, may also be used. Specific non-limiting examples of materials for the cathode layer 150 include, but are not limited to, barium, lithium, cerium, cesium, europium, rubidium, yttrium, magnesium, samarium, and alloys and combinations thereof.
  • The cathode layer 150 is usually formed by a chemical or physical vapor deposition process. In general, the cathode layer will be patterned, as discussed above in reference to the anode layer 110. If the device lies within an array, the cathode layer 150 may be patterned into substantially parallel strips, where the lengths of the cathode layer strips extend in substantially the same direction and substantially perpendicular to the lengths of the anode layer strips. Electronic elements called pixels are formed at the cross points (where an anode layer strip intersects a cathode layer strip when the array is seen from a plan or top view).
  • In other embodiments, additional layer(s) may be present within organic electronic devices. For example, a layer (not shown) between the buffer layer 120 and the EL layer 130 may facilitate positive charge transport, band-gap matching of the layers, function as a protective layer, or the like. Similarly, additional layers (not shown) between the EL layer 130 and the cathode layer 150 may facilitate negative charge transport, band-gap matching between the layers, function as a protective layer, or the like. Layers that are known in the art can be used. In addition, any of the above-described layers can be made of two or more layers. Alternatively, some or all of inorganic anode layer 110, the buffer layer 120, the EL layer 130, and cathode layer 150, may be surface treated to increase charge carrier transport efficiency. The choice of materials for each of the component layers may be determined by balancing the goals of providing a device with high device efficiency with the cost of manufacturing, manufacturing complexities, or potentially other factors.
  • The different layers may have any suitable thickness. In one embodiment, inorganic anode layer 110 is usually no greater than 500 nm, for example, 10-200 nm; buffer layer 120, is usually no greater than 250 nm, for example, 50-200 nm; EL layer 130, is usually no greater than 100 nm, for example, 50-80 nm; optional layer 140 is usually no greater than 100 nm, for example, 20-80 nm; and cathode layer 150 is usually no greater than 100 nm, for example, 1-50 nm. If the anode layer 110 or the cathode layer 150 needs to transmit at least some light, the thickness of such layer may not exceed 100 nm.
  • In organic light emitting diodes (OLEDs), electrons and holes, injected from the cathode 150 and anode 110 layers, respectively, into the EL layer 130, form negative and positively charged polar ions in the polymer. These polar ions migrate under the influence of the applied electric field, forming a polar ion exciton with an oppositely charged species and subsequently undergoing radiative recombination. A sufficient potential difference between the anode and cathode, usually less than 12 volts, and in many instances no greater than 5 volts, may be applied to the device. The actual potential difference may depend on the use of the device in a larger electronic component. In many embodiments, the anode layer 110 is biased to a positive voltage and the cathode layer 150 is at substantially ground potential or zero volts during the operation of the electronic device. A battery or other power source(s) may be electrically connected to the electronic device as part of a circuit but is not illustrated in FIG. 1.
  • In one embodiment, OLEDs comprising at least one buffer layer deposited from aqueous dispersions comprising at least one polythiophenes having Formula I(a) or Formula I(b) and at least one colloid-forming polymeric acids have been found to have improved lifetimes. The buffer layer may be deposited from an aqueous dispersion of polythiophene having Formula I(a) or Formula I(b) and fluorinated polymeric sulfonic acid colloids; in one embodiment the buffer layer is depositing using any solution processing technique and is an aqueous dispersion in which the pH has been adjusted to above about 3.5.
  • In one embodiment a pH neutral composition is used in at least one layer of an electronic device. In one OLED embodiment, the pH is adjusted so as to reduce etching of the ITO layer during device fabrication and hence much lower concentration of In and Sn ions diffusing into the polymer layers of the OLED. Since In and Sn ions are suspected to contribute to reduced operating lifetime this is a significant benefit. The lower acidity also reduces corrosion of the metal components of the display (e.g. electrical contact pads) during fabrication and over the long-term storage. PEDT/PSSA residues will interact with residual moisture to release acid into the displays with resulting slow corrosion.
  • Equipment used to dispense the acidic PEDT/PSSA needs to be specially designed to handle the strong acidity of PEDT/PSSA. For example, a chrome-plated slot-die coating-head used to coat the PEDT/PSSA onto ITO substrates was found to be corroding due to the acidity of the PEDT/PSSA. This rendered the head unusable since the coated film became contaminated with particles of chrome. Also, certain ink-jet print heads are of interest for the fabrication of OLED displays. They are used for dispensing both the buffer layer and the light-emitting polymer layer in precise locations on the display. These print-heads contain nickel mesh filters as an internal trap for particles in the ink. These nickel filters are decomposed by the acidic PEDT/PSSA and rendered unusable. Neither of these corrosion problems will occur with the aqueous polythiophene dispersions of the compositions in which the acidity has been lowered.
  • Furthermore, certain light-emitting polymers are found to be sensitive to acidic conditions, and their light-emitting capability is degraded if they are in contact with an acidic buffer layer. It is advantageous to use the aqueous dispersions of the compositions to form the buffer layer because the ability to adjust pH to a lower acidity or neutrality.
  • In one embodiment the fabrication of full-color or area-color displays using two or more different light-emitting materials becomes complicated if each light-emitting material requires a different cathode material to optimize its performance. Display devices are made up of a multiplicity of pixels which emit light. In multicolor devices there are at least two different types of pixels (sometimes referred to as sub-pixels) emitting light of different colors. The sub-pixels are constructed with different light-emitting materials. It is very desirable to have a single cathode material that gives good device performance with all of the light emitters. This minimizes the complexity of the device fabrication. When the buffer layer is made from the aqueous polythiophene dispersions of the composition, It may be possible to use a common cathode in multicolor devices while maintaining good device performance for each of the colors. The cathode can be made from any of the materials discussed above; and may be barium, overcoated with a more inert metal such as aluminum.
  • The layer in an organic electronic device comprising the composition may further comprise a layer of conductive polymer applied from aqueous solution or solvent. The conductive polymer can facilitate charge transfer and also improve coatability. Examples of suitable conductive polymers include, but are not limited to, polyanilines, polythiophenes, polydioxythiophene/polystyrenesulfonic acid, polyaniline/polymeric-acid-colloids such as those disclosed in co-pending application Ser. No. 10/669577 , polythiophene/polymeric-acid-colloids such as those disclosed in co-pending application Ser. No. 10/669494 , polypyrroles, polyacetylenes, and combinations thereof. The composition comprising such a layer may further comprise conductive polymers, and may also comprise dyes, carbon nanotubes, carbon nanoparticles, metal nanowires, metal nanoparticles, carbon fibers and particles, graphite fibers and particles, coating aids, organic and inorganic conductive inks and pastes, charge transport materials, semiconductive or insulating inorganic oxide particles, piezoelectric, pyroelectric, or ferroelectric oxide nano-particles or polymers, photoconductive oxide nanoparticles or polymers, dispersing agents, crosslinking agents and combinations thereof. These materials can be added to the composition either before or after polymerization of the monomer and/or before or after treatment with at least one ion exchange resin.
  • In one embodiment, described herein are thin film field effect transistors comprising electrodes comprising polythiophenes comprising at least one of the Formula I(a) or Formula I(b) and at least one colloid-forming polymeric sulfonic acid. For use as electrodes in thin film field effect transistors, the conducting polymers and the liquids for dispersing or dissolving the conducting polymers must be compatible with the semiconducting polymers and the solvents for the semiconducting polymers to avoid re-dissolution of either conducting polymers or semiconducting polymers. Thin film field effect transistor electrodes fabricated from conducting polymers should have a conductivity greater than 10 S/cm. However, electrically conducting polymers made with water soluble polymeric acids only provide conductivity in the range of ∼10-3 S/cm or lower. Thus, in one embodiment, the electrodes comprise polythiophene comprising at least one of the Formula I(a) or Formula I(b) and fluorinated colloid-forming polymeric sulfonic acids in combination with electrical conductivity enhancers such as metal nanowires, metal nanoparticles, carbon nanotubes, or the like. The compositions may be used in thin film field effect transistors as gate electrodes, drain electrodes, or source electrodes.
  • Another illustration of a use for the composition, is the thin film field effect transistors, is shown in FIG. 2. In this illustration, a dielectric polymer or dielectric oxide thin film 210 has a gate electrode 220 on one side and drain and source electrodes, 230 and 240, respectively, on the other side. Between the drain and source electrode, an organic semiconducting film 250 is deposited. New aqueous dispersions containing nanowires or carbon nanotubes are ideal for the applications of gate, drain and source electrodes because of their compatibility with organic based dielectric polymers and semiconducting polymers in solution thin film deposition. Since compositions as a colloidal dispersion, less weight percentage of the conductive fillers is required (relative to compositions containing water soluble polymeric sulfonic acids) to reach percolation threshold for a desired or high electrical conductivity.
  • In another embodiment, described herein are field effect resistance devices comprising one layer comprising at least one polythiophene having Formula I(a) or Formula I(b) and at least one colloid-forming polymeric sulfonic acids. The field effect resistance devices undergo a reversible change of resistance in the conducting polymer films when subjected to a pulse of gate voltage, as illustrated in pages 339-343, No. 2, 2002, Current Applied Physics.
  • In another embodiment, described herein are electrochromic displays comprising at least one layer comprising at least one polythiophene having Formula I(a) or Formula I(b) and at least one colloid-forming polymeric sulfonic acids. Electrochromic displays utilize change of color when thin film of the material is subjected to electrical potential. In one embodiment electrically conductive polythiophene/polymeric acid colloids of the composition are superior materials for this application because of the high pH of the dispersion, and the low moisture uptake and water non-dispersibility of dried solid films made from the dispersions.
  • In yet another embodiment, described herein are memory storage devices comprising silicon chips top-coated with a composition comprising at least one polythiophene having Formula I(a) or Formula I(b) and at least one colloid-forming polymeric sulfonic acids. For example, a write-once-read-many-times (WORM) memory is known in the arts (Nature, Page 166 to 169, vol 426, 2003). When information is recorded, higher voltages at certain points in the circuit grids of silicon chips destroys the polythiophene at those points to create "zero" bit data. The polythiophene at the untouched points remains electrically conductive and becomes "1" bit data.
  • In another embodiment, the new aqueous dispersions comprising at least one polythiophene having Formula I(a) or Formula I(b) and at least one colloid forming polymeric acid are used to form coatings for biosensor, electrochromic, andi-static, anti-corrosion, solid electrolyte capacitors, or electromagnetic shielding applications.
  • In another embodiment, the compositions can be used for antistatic coatings for plastic and cathode ray tubes, electrode materials for solid electrolyte capacitors, metal anti-corrosion coatings, through-hole plating of printed circuit boards, photodiodes, bio-sensors, photodetectors, rechargeable batteries, photovoltaic devices, and photodiodes. In addition, examples of other applications for the compositions can be found in, for example, Advanced Materials, page 490 to 491, vol. 12, No. 7, 2000.
  • In another embodiment, there are provided methods for producing, aqueous dispersions of polythiophene having Formula I(a) or Formula I(b) and at least one colloid-forming polymeric acid comprising polymerizing thiophene monomers having Formula II(a) or Formula II(b) in the presence of polymeric sulfonic acid colloids. The polymerization is carried out in the presence of water. The resulting reaction mixture can be treated with ion exchange resins to remove reaction byproducts and to adjust the pH of the dispersion. The composition and its uses will now be described in greater detail by reference to the following non-limiting examples. Examples 1, 2 and 9 do not form part of the invention.
  • EXAMPLES Example 1
  • This Example illustrates polymerization of (sulfonic acid-propylene-ether-methylene-3,4-dioxyethylene)thiophene in the presence of Nation®. A 25% (w/w) aqueous colloidal dispersion of perfluroethylenesulfonic acid with an EW of 990 is made using a procedure similar to the procedure in U.S. Patent No. 6,150,426 , Example 1, Part 2, except that the temperature is approximately 270°C. The dispersion is diluted with water to form a 12.5% (w/w) dispersion for the polymerization.
  • 63.87 g (8.06 mmoles of Nafion® monomer units) Nafion® aqueous colloidal dispersion, and 234.47 g deionized water will be massed into a 500 mL jacketed three-necked round bottom flask. The mixture will be stirred for 45 minutes before the addition of ferric sulfate and sodium persulfate. A stock solution of ferric sulfate will be made first by dissolving 0.0141 g ferric sulfate hydrate (97 %, Aldrich cat. #30,771-8) with deionized water to a total weight of 3.6363 g. 0.96g (0.0072 mmoles) of the ferric sulfate solution and 0.85 g (3.57 mmoles) sodium persulfate (Fluka, cat. # 71899) will be then placed into the reaction flask while the mixture will be stirred. The mixture will then be stirred for 3 minutes prior to addition of 0.8618 g (2.928 mmoles) of (sulfonic acid-propylene-ether-methylene-3,4-dioxyethylene)thiophene monomer. The monomer will be added to the reaction mixture while stirring. The polymerization will be allowed to proceed with stirring at about 20°C controlled by circulation fluid. The polymerization will be terminated in 16 hours by adding 8.91 g Lewatit® S100, a trade name from Bayer, Pittsburgh, PA, for sodium sulfonate of crosslinked polystyrene, and 7.70 g Lewatit® MP62 WS, a trade from Bayer, Pittsburgh, PA, for free base/chloride of tertiary/quaternary amine of crosslinked polystyrene. The two resins will be washed first before use with deionized water separately until there will be no color in the water. The resin treatment will proceed for 5 hrs. The resulting slurry will then be suction-filtered through a Whatman #54 filter paper.
  • Example 2
  • This Example illustrates polymerization of (propyl-ether-ethylene-3,4-dioxyethylene)thiophene in the presence of Nafion®. The Nafion® will be the same as in Example 1.
  • 63.87 g (8.06 mmoles of Nation monomer units) Nafion® aqueous colloidal dispersion, and 234.47 g deionized water will be massed into a 500 mL jacketed three-necked round bottom flask. The mixture will be stirred for 45 minutes before the addition of ferric sulfate and sodium persulfate. A stock solution of ferric sulfate will be made first by dissolving 0.0141 g ferric sulfate hydrate (97 %, Aldrich cat. #30,771-8) with deionized water to a total weight of 3.6363 g. 0.96 g (0.0072 mmoles) of the ferric sulfate solution and 0.85 g (3.57 mmoles) sodium persulfate (Fluka, cat. # 71899) will be then placed into the reaction flask while the mixture will be stirred. The mixture will then be stirred for 3 minutes prior to addition of 0.6685 g (2.928 mmoles) of (propyl-ether-ethylene-3,4-dioxyethylene)thiophene monomer. The monomer will be added to the reaction mixture while stirring. The polymerization will be allowed to proceed with stirring at about 20°C controlled by circulation fluid. The polymerization will be terminated in 16 hours by adding 8.91 g Lewatit® S100, a trade name from Bayer, Pittsburgh, PA, for sodium sulfonate of crosslinked polystyrene, and 7.70 g Lewatit® MP62 WS, a trade from Bayer, Pittsburgh, PA, for free base/chloride of tertiary/quaternary amine of crosslinked polystyrene. The two resins will be washed first before use with deionized water separately until there will be no color in the water. The resin treatment will proceed for 5 hrs. The resulting slurry will then be suction-filtered through a Whatman #54 filter paper.
  • Example 3
  • This example illustrates slow injection of both ethylenedioxythiophene ("EDT") monomer and oxidizing agent solution into the reaction mixture containing iron(III) sulfate catalyst, water, Nafion® and HCl co-acid. The Nafion® used is the same as in Example 1.
  • In a 2000 mL reaction kettle are put 715 g of 12% solid content aqueous Nation dispersion (82 mmol SO3 groups), 1470 g water, 0.5 g (0.98 mmol) iron(III)sulfate (Fe2(SO4)3), and 1406 µL of 37% HCl (18.1 mmol). The reaction mixture is stirred for 15 minutes at 200 RPM using an overhead stirrer fitted with a double stage propeller type blade before addition of 7.78 g (32.8 mmol) sodium persulfate (Na2S2O8) in 60 mL of water, and 3.17 mL ethylenedioxythiophene (EDT). The addition is started from separate syringes using addition rate of 0.9 mUh for Na2S2O8/water and 50 µL/h for EDT while continuously stirring at 200 RPM. EDT addition is accomplished by placing the monomer in a syringe connected to a Teflon® tube that leads directly into the reaction mixture. The end of the Teflon® tube connecting the Na2S2O8/water solution is placed above the reaction mixture such that the injection involves individual drops falling from the end of the tube such that the injection is gradual. The reaction is stopped 2 h after the addition of monomer has finished by adding 170 g of each Lewatit MP62WS and Lewatit Monoplus S100 ion-exchange resins, and 225 g of n-propanol to the reaction mixture and stirring it further for 4 h at 150 RPM. The ion-exchange resin is finally filtered from the solution using Whatman No. 54 filter paper. pH of the dispersion is 4 and dried films derived from the dispersion have conductivity of 1.4x10-4S/cm at room temperature.
  • Analysis by an Atomic Force Microscope (AFM) of films resulting from spin-coating dispersion onto ITO substrates revealed that all particulates in the film were smaller than 60 nm in height (multiple 50x50 µm scans). In comparison, films spun from dispersions made using procedures where all of the monomer is rapidly added in one portion, have large count of particles up to 200 nm tall and up to 500 nm wide.
  • Organic light emitting diodes (OLEDs) were fabricated to the following specifications: 6x6" substrates containing patterned indium-tin-oxide anodes, were cleaned in an oxygen plasma (300 W) for 10 minutes. Then approximately 75 nm thick film of the buffer was spun followed by baking at 130°C on a hotplate for 10 minutes. After cooling down to room temperature, the plate was spun with approximately 75 nm thick film of Lumination Green 1303 electroluminescent polymer from Dow Chemicals (from 1 % w/v solution in p-Xylene) in air. Following the baking of the electroluminescent film at 130°C in a vacuum oven for 40 minutes, a cathode consisting of 4 nm of Ba and 500 nm of Al was thermally evaporated at pressure less then 10-6Torr. Encapsulation of the devices was achieved by bonding a glass slide on the back of the devices using a UV-curable epoxy resin.
  • The resulting devices (16 devices total with 300 mm2 active area) had efficiency of 19.2 ± 0.5 cd/A @ 1000 cd/m2 at room temperature and a rectification ratio of 1000 at ±5V. Five devices were stressed with a constant current of 16.2 mA (approximately 900 cd/m2) at 80°C. After 1000 h the light output had decreased on average by 32% or ∼600 cd/m2.
  • Example 4
  • This example illustrates slow injection of both EDT monomer and oxidizing agent solution into the reaction mixture containing iron(III) sulfate catalyst, water, Nafion® and H2SO4 co-acid. The Nafion® is the same as in Example 1.
  • In a 2000mL reaction kettle are put 715g of 12% solid content aqueous Nafion® (82mmol SO3 groups) dispersion, 1530g water, 0.5g (0.98mmol) iron(III)sulfate (Fe2(SO4)3), and 1011µL of concentrated H2SO4 (18.1 mmol). The reaction mixture is stirred for 15min at 276RPM using an overhead stirrer fitted with a double stage propeller type blade, before addition of 8.84g (37.1 mmol) sodium persulfate (Na2S2O8) in 60mL of water, and 3.17mL ethylenedioxythiophene (EDT) is started from separate syringes using addition rate of 4.2mUh for Na2S2O8/water and 224µL/h for EDT while continuously stirring at 276RPM. The addition of EDT is accomplished by placing the monomer in a syringe connected to a Teflon® tube that leads directly into the reaction mixture. The end of the Teflon® tube connecting the Na2S2O8/water solution was placed above the reaction mixture such that the injection involved individual drops falling from the end of the tube. The reaction is stopped 7 hours after the addition of monomer has finished by adding 170g of each Lewatit MP62WS and Lewatit Monoplus S100 ion-exchange resins, and 225g of n-propanol to the reaction mixture and stirring it further for 7hours at 130RPM. The ion-exchange resin is finally filtered from the dispersion using Whatman No. 54 filter paper. The pH of the dispersion is ∼4 and dried films derived from the dispersion have conductivity of 2.6x10-5S/cm at room temperature.
  • Organic light emitting diodes (OLEDs) are fabricated to the following specifications: 6x6" substrates containing patterned indium-tin-oxide anodes partially covered with 600nm thick photo-resist for device area definition, were cleaned in an UV-Ozone oven for 10min. Then approximately 75nm thick film of the buffer layer from the PEDOT/ Nafion® made above is spun followed by baking at 130°C on a hotplate for 10min. After cooling down to room temperature, the plate is spun with approximately 75nm thick film of Lumination Green 1303 electroluminescent polymer from Dow Chemicals (from 1% w/v solution in p-xylene) in air. Following the baking of the electroluminescent film at 130°C in a vacuum oven for 40min, a cathode consisting of 4nm of Ba and 500nm of Al is thermally evaporated at pressure less than 10-6Torr. Encapsulation of the devices is achieved by bonding a glass slide on the back of the devices using a UV-curable epoxy resin.
  • The resulting devices (25mm2 active area) have an efficiency of 20±1cd/A @ 1000cd/m2 and a rectification ratio of 13000 @ ±5V. Six devices are stressed with a constant current of 50mA/cm2 (approximately 8,000cd/m2) at 25°C. In 220h the luminance drops to half the initial value.
  • Example 5
  • This example illustrates the effect of the addition of ethylene glycol on the conductivity of as-synthesized PEDOT/Nafion®:
    • An aqueous PEDT/Nafion®. used for this example was prepared as follows:
      • 0.309ml (2.902 mmoles) of Baytron-M (a trade name for 3,4ethyylenedioxythiophene) from H. C. Starck GmbH (Leverkusen, Germany) was predissolved in 229.12 g deionized water at 20°C for one hour in a 500 ml jacketed three-necked round bottom flask equipped with a stirrer at a speed of 175RPM. 69.52g (8.0mmoles of Nafion® monomer units) DE1021 (E.I. du Pont de Nemours and Company (Wilmington, DE, USA; EW: 999 g/mole acid) Nafion® was then massed into the mixture. As soon as the Nafion® was added, 0.84g (3.538 mmoles) sodium persulfate pre-dissoved in 10 g deionized water was added to the reaction vessel. 0.95g (7.1 mmoles) of a stock solution of ferric sulfate was then added. The stock solution of ferric sulfate was made first by dissolving 0.0141 g ferric sulfate hydrate (97 %, Aldrich cat. #30,771-8) with deionized water to a total weight of 3.6363 g. The polymerization was allowed to proceed with stirring at about 20 °C controlled by circulation fluid. The polymerization liquid started to turn blue in 13 minutes. The reaction was terminated in 14 hours by adding 11.03 g Lewatit® S100, a trade name from Bayer, Pittsburgh, PA, for sodium sulfonate of crosslinked polystyrene, and 11.03g Lewatit® MP62 WS, a trade from Bayer, Pittsburgh, PA, for free base/chloride of tertiary/quaternary amine of crosslinked polystyrene. The two resins were washed first before use with deionized water separately until there was no color in the water. The resin treatment proceeded for about 6 hrs. The resulting slurry was then suction-filtered through a Whatman #54 filter paper. It went through the filter paper very fast. Yield was 268 g. Solid % was about 2.8%(w/w) based on added polymerization ingredients. pH of the aqueous PEDT/Nafion® was determined to be 4.64 with a 315 pH/lon meter from Corning Company (Corning, New York, USA).
  • A couple drops of the dispersion made above were spread on a microscope slide, which was left dried in ambient conditions before placed in a vacuum oven set at 90°C for 30 minutes. The oven was constantly fed with a small amount of flowing nitrogen. Once baked, the dried films having thickness of ∼ 2µm were painted with approximately 0.4 cm parallel vertical lines with a separation of about 0.15 cm between each two parallel lines. The thickness was measured using a Surface Profilier (model# Alpha-Step 500, from Tencor Instrument, San Jose, CA, USA). Resistance was then measured at ambient temperature by applying voltage between 1 and -1 volt using a Keithley 2420 Source Meter. Average conductivity of five samples was 1.1x10-5S/cm. It should be pointed out that the films used for resistance measurement do not re-disperse in water.
  • 9.5021g of the aqueous dispersion, which contains 0.266g solid and 9.2361g water, was mixed with 0.499g ethylene glycol (Across Organics, Cat# 295530010) and stirred for 3 hours. It formed a smooth dispersion, which contains 2.7% (w/w) PEDOT/Nafion®, and 5.0%(w/w) ethylene glycol. Couple drops of the dispersion made above were spread on a microscope slide. The films left dried on a hot plate set at ∼50°C in ambient conditions before placed in a vacuum oven set at 90°C for 50 minutes. The oven was constantly fed continuously with a small amount of flowing nitrogen. Once baked, the dried films having thickness of ∼ 6µm were painted with approximately 0.4 cm parallel vertical lines with a separation of about 0.15 cm between each two parallel lines. Resistance was then measured at ambient temperature by applying voltage between 1 and -1 volt. Average conductivity of four samples was 2.9x10-4S/cm. The conductivity is about 30 times the conductivity of the films made from as-synthesized PEDOT/Nafion®.
  • 7.9981g of the aqueous dispersion, which contains 0.2239g solid and 7.7742g water, was mixed with 2.0154g ethylene glycol (Across Organics, Cat# 295530010) and stirred for 3 hours. It formed a smooth dispersion which contains 2.2% (w/w) PEDOT/Nafion® and 20.1%(w/w) ethylene glycol. Films preparation and resistance are as described for 5% ethylene glycol. Once baked, the dried films having thickness of ∼ 3µm were painted with approximately 0.4 cm parallel vertical lines with a separation of about 0.152cm between each two parallel lines. Resistance was then measured at ambient temperature by applying voltage between 1 and -1 volt. Average conductivity of four samples was 4.6x10-4S/cm. The conductivity is about 46 times the conductivity of the films made from as-synthesized PEDOT/Nafion®.
  • Example 6
  • This example illustrates one ink-jetting application of PEDOT/Nafion® with added ethylene glycol:
    • The preparation of one of the four large batches (1,700g) of aqueous PEDOT/Nafion® dispersion, which was combined for microfluidization for particle size reduction, is described below. The Nafion® used for the polymerization is the same as in Example 1 with an EW of 1050.
    • 366.1 g (46.13 mmoles of Nafion® monomer units) Nafion® aqueous colloidal dispersion, and 1693.7 g deionized water was massed into a 2000 ml jacketed three-necked round bottom flask. The mixture was stirred for 2 hrs at a stirring speed of 425RPM before the addition of ferric sulfate and sodium persulfate. A stock solution of ferric sulfate was made first by dissolving 0.1017g ferric sulfate hydrate (97 %, Aldrich cat. #30,771-8) with deionized water to a total weight of 19.4005g. 4.07g (0.0413 mmoles) of the ferric sulfate solution and 4.88g (40.99 mmoles) sodium persulfate (Fluka, cat. # 71899) were then placed into the reaction flask while the mixture was being stirred. The mixture was then stirred for 4 minutes prior to addition of 1.790ml (16.796 mmoles) of Baytron-M (a trade name for 3,4-ethyylenedioxythiophene H. C. Starck, LeverKusen, Germany) was added to the reaction mixture while stirring. The polymerization was allowed to proceed with stirring at about 20 °C controlled by circulation fluid. The polymerization liquid started to turn blue in 13 minutes. The reaction was terminated in 7 hours by adding 44.17g Lewatit® S100, a trade name from Bayer, Pittsburgh, PA, for sodium sulfonate of crosslinked polystyrene, and 48.80g Lewatit® MP62 WS, a trade from Bayer, Pittsburgh, PA, for free base/chloride of tertiary/quaternary amine of crosslinked polystyrene. The two resins were washed first before use with deionized water separately until there was no color in the water. The resin treatment proceeded for 5 hrs. The resulting slurry was then suction-filtered through a Whatman #54 filter paper. It went through the filter paper very fast. Solid % was about 3.0 %(w/w). Four batches made in the same manner as described above were combined and microfluidized with a Microfluidizer Processor M-110Y (Microfluidics, Massachusetts, USA) using a pressure of 5,000-7,000psi for five passes. The diameter of first pressure chamber and second pressure chamber is 200µm (H30Z model).
  • Viscosity and surface tension are two most critical physical properties for ink-jet printing. They effect drop formation, jet stability, substrate wetting, spreading and leveling as well as drying phenomena. Viscosity of the 3 % PEDOT/Nafion® is about 1.9 cp at 60 rpm and the viscosity of 1% is about 0.9 cp at 60 rpm. The obtained printing surface is not very smooth. The viscosity is too low and the surface tension is too high for effective ink-jet printing. Therefore, ethylene glycol was added as described below, which should improve conductivity as demonstrated in Example 5, increase viscosity, lower the surface tension of PEDOT/Nafion®.
  • 8.0 ml (density ∼1.008g/ml) of the microfluidized aqueous dispersion was added with 14 ml deionized water and 4.0 ml ethylene glycol (density ∼1.113g/ml; Acros Organics, Cat# 295530010). The composition contains 0.91 % (w/w) PEDOT/Nafion®, 16.9% ethylene glycol. The ink was filtered through HV filter after mixed well. Viscosity of the ink was measured to be 2.45 cps at 60rpm.
  • Microfab (single-nuzzle system) was used for ink-jet printing. A 30 um tip was back-flushed with DI water and blow-dried with N2. The ink-jetting head was set-up, and a stable and clean drop was obtained using 15 volts with 45 us dwell time. A full-drizzle 1 um undercut plate (5206) was treated with UV-Ozone for 15 minutes, then treated with CF4 plasma for 3 minutes. The plate was placed at the printing stage at room temperature. Display 1, 2, 3, 4 were printed. For Display1, Row 1 to Row 5 were printed with 7 drops per pixel, R6 to R 10 were printed with 8 drops per pixel, R16 to R 20 were printed with 9 drops per pixel, and R 21 to R 25 were printed with 10 drops per pixel. For Display 4, R11 to R15 were printed with 11 drops per pixel, R21 to R25 were printed 12 drops per pixel, R26 to R 30 were printed 13 drops per pixel, and R 31 to R 35 were printed with 14 drops per pixel. Then the plate was heated to 40°C, Display 5, 6, and 7 were printed with 8drops, 10 drops, 12 drops per pixel, respectively. The plate after printed was baked at 130C under vacuum for 30 minutes.
  • 0.91% PEOT/Nafion® with 16.9% ethylene glycol added gave higher viscosity (2.45cps at 60rpm) than that of 1% PEDOT/ Nafion® aqueous ink (0.9cps at 60rpm). 0.91 % PEDOT /Nafion®/EG ink gave better printability than 1% aqueous Nafion® aqueous system. Stable and clean drops without satellites were obtained easily with low voltage (15v). Nuzzle stability was also improved by adding 16.9% ethylene glycol. Smooth surface was obtained with PEDOT/ Nafion®/EG ink.
  • Example 7
  • This Example illustrates the preparation of an aqueous dispersion of PEDT/Nafion® and the effect of the addition of methanol on electrical conductivity and particle size.
  • 73.46g (8.81 mmoles) Nafion® aqueous colloidal dispersion and 224.8 g deionized water was massed into a 500 ml jacketed three-necked round bottom flask. Nafion® DE1020 (a commercial perfluoroethylenesulfonic acid from E. I. du Pont de Nemours and Company, Wilmington, DE) was an 11.4% (w/w) aqueous colloidal dispersion having an EW of 951g/acid equivalent. The mixture was allowed to stir for 20 °C for 30 minutes. 0.469ml (4.40 mmoles) of Baytron-M (a trade name for 3,4-ethyylenedioxythiophene from H.C. Starck, MA, USA) was added to the Nafion®/water mixture and was allowed to stir for 15 more minutes before addition of ferric sulfate and sodium persulfate. 1.10g (4.62mmoles) sodium persulfate (Fluka, cat. # 71899) was first dissolved in 5g deionized water in a glass vial and then transferred to the ration mixture while the mixture was being stirred. A stock solution of ferric sulfate was made first by dissolving 0.0141 g ferric sulfate hydrate (97 %, Aldrich cat. #30,771-8) with deionized water to a total weight of 3.6363 g. 1.44g (0.0108mmoles) of the ferric sulfate stock solution added to the reaction flask immediately after the addition of the ferric sulfate solution. The polymerization was allowed to proceed with stirring at about 20 °C controlled by circulation fluid. The polymerization liquid started to turn blue in 13 minutes. The reaction was terminated in 12 hours by adding 9.61g Lewatit® S100, a trade name from Bayer, Pittsburgh, PA, for sodium sulfonate of crosslinked polystyrene, and 9.61g Lewatit® MP62 WS, a trade from Bayer, Pittsburgh, PA, for free base/chloride of tertiary/quaternary amine of crosslinked polystyrene. The two resins were washed first before use with deionized water separately until there was no color in the water. The resin treatment proceeded for 10 hrs. The resulting slurry was then suction-filtered through a Buchner Funnel containing two pieces of Whatman #4 filter paper. It went through the filter paper very fast. Yield was 290g. Solid % was about 3.0 %(w/w) based on added polymerization ingredients. pH of the aqueous PEDT/Nafion® was determined to be 4.95 with a 315 pH/Ion meter from Corning Company (Corning, New York, USA). Electrical conductivity of the as-made dispersion was determined to be 2.6x10-6 S/cm using a two-probe resistance measurement technique. A small portion of the dispersion was added with 10% (w/w) methanol. Conductivity was determined to be 3.8x10-6 S/cm, which shows that conductivity remains similar with addition of the methanol. However, the effect on particle size count, measured with an Accusizer (Model 780A, Particle Sizing Systems, Santa Barbara, CA), is pronounced as illustrated in Table I, which shows number of particles per one mL dispersion, which have particle size greater than 0.75µm, 1.51µm, and 2.46µm, respectively. The data clearly shows that methanol not only stabilizes the PEDT/Nafion® particles, but also reduces number of large particles substantially. Table 1
    Methanol (10%) >0.75 µm >1.51 µm >2.46 µm
    Methanol (10%) >0.75 µm >1.51 µm >2.46 µm
    Without (As-made) 355,488 57,448 17,983
    Without (14 days) 400,122 69,948 21, 849
    With (3 hr) 262,795 38,816 10,423
    With (27 hr) 245,573 34,586 9,477
    With (14 days) 18,864 8,252 4,233
  • Example 8
  • This Example illustrates the preparation of an aqueous dispersion of PEDT/Nafion® and the effect of the addition of n-propanol on particle size. The Nafion® used was the same as in Example 1.
  • In a 500mL reaction kettle are put 85.9g of 12% solid content aqueous Nafion® dispersion (9.8mmol SO3H groups), 313g water, 1.86g (7.8mmol) sodium perisulfate (Na2S2O8), and 0.084g (0.125mmol) iron(III)sulfate (Fe2(SO4)3. The reaction mixture is stirred for 15min at 180RPM using a propeller type blade before addition of 0.695mL (6.5mmol) ethylenedioxythiophene (EDT) is started using addition rate of 20µL/h while continuously stirring at 180RPM. The addition of EDT is accomplished by placing the monomer in a syringe connected to a Teflon® tube that leads directly into the reaction mixture. The reaction is stopped 36h after the addition of monomer has finished by adding 25g of each Lewatit MP62WS and Lewatit Monoplus S100 ion-exchange resins to the reaction mixture and stirring for 3h at 180RPM. The ion-exchange resin is finally filtered from the solution using Whatman No. 54 filter paper. Portion of the dispersion is diluted by 10%w/w with n-propanol. After 60h, particle count, measured an Accusizer (Model 780A, Particle Sizing Systems, Santa Barbara, CA), of PEDT/ Nafion® particles of the dispersion prior to and after addition of n-propanol is shown in Table II and Figure 1. The data clearly shows that n-propanol, a low boiling liquid, has reduced the number of large PEDT/Nafion® particles substantially. Table 2
    n-Propanol (10%) >0.75 µm >1.51 µm >2.46 µm
    Without 2,430,000 593,000 100,000
    With 211,000 33,000 8000
  • EXAMPLE 9
  • This Example illustrates preparation of an aqueous dispersion of PEDT/Nafion®. The Nafion® used was the same as in Example 1.
  • 63.89g (8.07 mmoles of Nafion® monomer units) Nafion® (990 EW) aqueous colloidal dispersion (12.5 %, w/w) and 234.79 g deionized water was massed into a 500 ml jacketed three-necked round bottom flask. The mixture was stirred for 45 minutes before addition of ferric sulfate and sodium persulfate. A stock solution of ferric sulfate was made first by dissolving 0.0135 g ferric sulfate hydrate (97 %, Aldrich cat. #30,771-8) with deionized water to a total weight of 3.5095 g. 0.97g (0.0072 mmoles) of the ferric sulfate solution and 0.85 g (3.57 mmoles) sodium persulfate (Fluka, cat. # 71899) were then placed into the reaction flask while the mixture was being stirred. The mixture was then stirred for 3 minutes prior to addition of 0.312 ml (2.928 mmoles) of Baytron-M (a trade name for 3,4-ethylene dioxythiophene from Bayer, Pittsburgh, PA) to the reaction mixture while stirring. The polymerization was allowed to proceed with stirring at about 20°C controlled by circulation fluid. The polymerization liquid turned medium dark blue in half an hour. The reaction was terminated after 19.6 hours by adding 8.97 g Lewatit® S100 (a trade name from Bayer, Pittsburgh, PA, for sodium sulfonate of crosslinked polystyrene) and 7.70 g Lewatit® MP62 WS (a trade from Bayer, Pittsburgh, PA, for free base/chloride of tertiary/quaternary amine of crosslinked polystyrene). The two resins were washed first before use with deionized water separately until there was no color in the water. The resin treatment was allowed to proceed for 5 hrs. The resulting slurry was then suction-filtered through a Whatman #54 filter paper. It went through the filter paper readily. The yield was 273.7 g. The solid % was about 3.1 %(w/w) based on added polymerization ingredients.
  • EXAMPLE 10
  • This example illustrates the effect of added co-dispersing liquid on the surface tension of the PEDT/Nafion® dispersion.
  • The surface tension of the aqueous PEDT/Nafion® from Example 9, without any co-dispersing liquid, was measured with a FTA T10 Tensiometer Model 1000 IUD (KSV Instruments, Finland) and determined to be 73 milliN/meter at 19.5 °C.
  • To determine effect of the co-dispersing liquid on the surface tension, 25.436 ml of the PEDT/Nafion® from Example 1 was mixed with 1.4781 ml n-propanol (n-PA) and 2.051 ml 1-methoxy-2-propanol (1M2P), which constitutes 87.8 V.% PEDT/Nafion®, 5.1 V.% n-PA, and 7.1 V.% 1M2P. The mixture of dispersion and co-dispersing liquid was very smooth having no indication of precipitation. The surface tension of the dispersion with co-dispersing liquid was determined to be 42.24 mN/m. The lower surface tension of the new dispersion indicates its increased wetability and ease of coating.
  • EXAMPLE 11
  • This example illustrates effect of co-dispersing liquids on light emitting diode performance.
  • The aqueous PEDT/Nafion® dispersion prepared in Example 9 and the co-dispersing liquid mix described in Example 10 were tested for light emission properties. The glass/ITO substrates (30mmx30mm) having ITO thickness of 100 to 150 nm and 15mmx20mm ITO area for light emission were cleaned and subsequently treated with oxygen plasma. The aqueous PEDT/ Nafion® dispersions with and without the co-dispersing liquids were spin-coated onto the ITO/glass substrates. The thickness was 75 nm for both with and without the dispersing liquids. The PEDT/Nafion® coated ITO/glass substrates were dried in vacuum at 90 °C for 30 minutes. The PEDT/ Nafion® layer was then top-coated with HS670 blue emitting polymer from Covion Organic Semiconductor GmbH (Frankfurt, Germany). The thickness of the EL layer was approximately 75 nm. The film thickness was measured with a TENCOR 500 Surface Profiler. The HS670 top-coated structure was then baked at 100 °C for 10 minutes in vacuum. Ba and Al layers were vapor deposited on top of the EL layers under a vacuum of 1 x 10-6 torr. The final thickness of the Ba layer was 30 Å; the thickness of the Al layer was 4000 Å. The devices made from PEDT/Nafion® with the co-dispersing liquids have a higher efficiency (6.0 Cd/A) than the devices made without the co-dispersing liquids in the aqueous PEDT/Nafion® (4.5 Cd/A) although they have similar voltage (∼4.2volt). Device luminance and voltage as a function of time are shown in FIG. 11. The devices made with the new dispersions, which contain a co-dispersing liquid, have a longer half-life at 80°C (100 hrs) than the devices made from dispersions of aqueous PEDT/Nafion® alone (50, hrs.).
  • Claims (1)

    1. A method of forming a composition comprising an aqueous dispersion of at least one polythiophene, at least one colloid-forming polymeric acid and at least one co-dispersing liquid, wherein said polythiophene comprises the Formula I(a) or Formula I(b):
      Figure imgb0005
      wherein:
      R" is the same or different at each occurrence and is selected from hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, sulfonate, and urethane, with the proviso that at least one R" is not hydrogen,
      m is 2 or 3, and
      n is at least about 4; or
      Figure imgb0006
      wherein:
      R'1 and R1 are independently selected from hydrogen and alkyl, or
      R'1 and R1 taken together form an alkylene chain having 1 to 4 carbon atoms, which may optionally be substituted by alkyl or aromatic groups having 1 to 12 carbon atoms, or a 1,2- cyclohexylene radical, and
      n is at least about 4;
      wherein said colloid-forming polymer acid comprises a fluorinated polymeric sulfonic acid; and
      wherein the aqueous dispersion has a pH of 4 to 8;
      said method comprising:
      polymerizing at least one thiophene monomer in the presence of the at least one colloid-forming polymeric acid, one oxidizing agent, and one polymerisation catalyst,
      wherein said thiophene monomer has Formula II(a) or Formula II(b):
      Figure imgb0007
      wherein:
      R" is the same or different at each occurrence and is selected from hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, and urethane, with the proviso that at least one R" is not hydrogen,
      m is 2 or 3;
      R'1 and R1 are independently selected from hydrogen and alkyl, or
      R'1 and R1 taken together form an alkylene chain having 1 to 4 carbon atoms, which may optionally be substituted alkyl or aromatic having 1 to 12 carbon atoms, or a 1,2 cyclohexylene radical; and
      adding the at least one co-dispersing liquid after the thiophene polymerisation.
    EP20040750548 2002-09-24 2004-04-22 Water dispersible polythiophenes made with polymeric acid colloids Active EP1615971B2 (en)

    Priority Applications (4)

    Application Number Priority Date Filing Date Title
    US46437003 true 2003-04-22 2003-04-22
    US10669494 US7431866B2 (en) 2002-09-24 2003-09-24 Water dispersible polythiophenes made with polymeric acid colloids
    US10802704 US7390438B2 (en) 2003-04-22 2004-03-17 Water dispersible substituted polydioxythiophenes made with fluorinated polymeric sulfonic acid colloids
    PCT/US2004/012564 WO2004094501A3 (en) 2003-04-22 2004-04-22 Water dispersible polythiophenes made with polymeric acid colloids

    Publications (3)

    Publication Number Publication Date
    EP1615971A2 true EP1615971A2 (en) 2006-01-18
    EP1615971B1 EP1615971B1 (en) 2009-06-03
    EP1615971B2 true EP1615971B2 (en) 2017-12-27

    Family

    ID=33314256

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP20040750548 Active EP1615971B2 (en) 2002-09-24 2004-04-22 Water dispersible polythiophenes made with polymeric acid colloids

    Country Status (3)

    Country Link
    US (2) US7390438B2 (en)
    EP (1) EP1615971B2 (en)
    WO (1) WO2004094501A3 (en)

    Families Citing this family (95)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP1606846B1 (en) * 2003-03-24 2010-10-27 Konarka Technologies, Inc. Photovoltaic cell with mesh electrode
    US7462298B2 (en) 2002-09-24 2008-12-09 E.I. Du Pont De Nemours And Company Water dispersible polyanilines made with polymeric acid colloids for electronics applications
    CA2499377A1 (en) 2002-09-24 2004-04-08 E. I. Du Pont De Nemours And Company Water dispersible polythiophenes made with polymeric acid colloids
    US7317047B2 (en) 2002-09-24 2008-01-08 E.I. Du Pont De Nemours And Company Electrically conducting organic polymer/nanoparticle composites and methods for use thereof
    US7390438B2 (en) 2003-04-22 2008-06-24 E.I. Du Pont De Nemours And Company Water dispersible substituted polydioxythiophenes made with fluorinated polymeric sulfonic acid colloids
    EP2341118A1 (en) 2002-09-24 2011-07-06 E. I. du Pont de Nemours and Company Electrically conducting organic polymer/nanoparticle composites and methods for use thereof
    US7686978B2 (en) * 2003-09-24 2010-03-30 E. I. Du Pont De Nemours And Company Method for the application of active materials onto active surfaces and devices made with such methods
    US7622844B1 (en) * 2003-12-30 2009-11-24 Hipercon, Llc Metal fiber brush interface conditioning
    US7923109B2 (en) * 2004-01-05 2011-04-12 Board Of Regents, The University Of Texas System Inorganic nanowires
    US20050175861A1 (en) * 2004-02-10 2005-08-11 H.C. Starck Gmbh Polythiophene compositions for improving organic light-emitting diodes
    US7351358B2 (en) 2004-03-17 2008-04-01 E.I. Du Pont De Nemours And Company Water dispersible polypyrroles made with polymeric acid colloids for electronics applications
    US7250461B2 (en) 2004-03-17 2007-07-31 E. I. Du Pont De Nemours And Company Organic formulations of conductive polymers made with polymeric acid colloids for electronics applications, and methods for making such formulations
    US7338620B2 (en) * 2004-03-17 2008-03-04 E.I. Du Pont De Nemours And Company Water dispersible polydioxythiophenes with polymeric acid colloids and a water-miscible organic liquid
    US20050222333A1 (en) * 2004-03-31 2005-10-06 Che-Hsiung Hsu Aqueous electrically doped conductive polymers and polymeric acid colloids
    US7455793B2 (en) * 2004-03-31 2008-11-25 E.I. Du Pont De Nemours And Company Non-aqueous dispersions comprising electrically doped conductive polymers and colloid-forming polymeric acids
    US8147962B2 (en) 2004-04-13 2012-04-03 E. I. Du Pont De Nemours And Company Conductive polymer composites
    US20060065889A1 (en) * 2004-09-30 2006-03-30 Pierre-Marc Allemand Compositions for making organic thin films used in organic electronic devices
    US7838688B2 (en) * 2004-12-30 2010-11-23 E.I. Du Pont De Nemours And Company Derivatized 3,4-Alkylenedioxythiophene monomers, methods of making them, and use thereof
    JP2008526768A (en) * 2004-12-30 2008-07-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Organic metal complex
    US20080121846A1 (en) * 2004-12-30 2008-05-29 E.I. Du Pont De Nemours And Company Electrically Conductive Polymers
    US7670506B1 (en) 2004-12-30 2010-03-02 E. I. Du Pont De Nemours And Company Photoactive compositions for liquid deposition
    KR101213484B1 (en) 2005-05-19 2012-12-20 삼성디스플레이 주식회사 Conductive polymer composition and an organic photoelectric device employing the same
    GB0510382D0 (en) * 2005-05-20 2005-06-29 Cambridge Display Tech Ink jet printing compositions in opto-electrical devices
    US7476603B2 (en) * 2005-06-07 2009-01-13 Hewlett-Packard Development Company, L.P. Printing conductive patterns using LEP
    EP1896515A4 (en) * 2005-06-27 2010-03-10 Du Pont Electrically conductive polymer compositions
    WO2007002683A3 (en) * 2005-06-27 2007-09-20 Du Pont Electrically conductive polymer compositions
    KR101294892B1 (en) * 2005-06-27 2013-08-09 이 아이 듀폰 디 네모아 앤드 캄파니 Electrically Conductive Polymer Compositions
    WO2007002740A3 (en) * 2005-06-28 2009-04-16 Du Pont Buffer compositions
    CN101208369B (en) 2005-06-28 2013-03-27 E.I.内穆尔杜邦公司 High work function transparent conductor
    JP2008547186A (en) * 2005-06-28 2008-12-25 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Bilayer anode
    US20070077451A1 (en) * 2005-09-30 2007-04-05 Pierre-Marc Allemand Neutralized anode buffer layers to improve processing and performances of organic electronic devices
    KR100684913B1 (en) * 2005-10-06 2007-02-13 연세대학교 산학협력단 Preparation method of polythiophene nanoparticles and derivatives thereof by oxidation polymerization of thiophene emulsion in aqueous phase
    KR101193180B1 (en) * 2005-11-14 2012-10-19 삼성디스플레이 주식회사 A conducting polymer composition and an electronic device employing the layer obtained from the conducting polymer composition
    DE102005060159A1 (en) * 2005-12-14 2007-06-21 H. C. Starck Gmbh & Co. Kg Transparent polymeric electrode for electro-optical structures
    US8440324B2 (en) 2005-12-27 2013-05-14 E I Du Pont De Nemours And Company Compositions comprising novel copolymers and electronic devices made with such compositions
    US7807992B2 (en) * 2005-12-28 2010-10-05 E.I. Du Pont De Nemours And Company Organic electronic device having dual emitter dopants
    US7785489B2 (en) * 2005-12-28 2010-08-31 E.I. Du Pont De Nemours And Company Solvent formulations for solution deposition of organic materials onto low surface energy layers
    US20070170401A1 (en) * 2005-12-28 2007-07-26 Che-Hsiung Hsu Cationic compositions of electrically conducting polymers doped with fully-fluorinated acid polymers
    EP2412699A1 (en) * 2005-12-28 2012-02-01 E.I. Du Pont De Nemours And Company Compositions comprising novel compounds and electronic devices made with such compositions
    US7838627B2 (en) 2005-12-29 2010-11-23 E. I. Du Pont De Nemours And Company Compositions comprising novel compounds and polymers, and electronic devices made with such compositions
    DE102006002798A1 (en) 2006-01-20 2007-08-09 H. C. Starck Gmbh & Co. Kg Polythiophenformulierungen to improve organic light emitting diodes
    US8470208B2 (en) 2006-01-24 2013-06-25 E I Du Pont De Nemours And Company Organometallic complexes
    US8216680B2 (en) 2006-02-03 2012-07-10 E I Du Pont De Nemours And Company Transparent composite conductors having high work function
    US20070246689A1 (en) * 2006-04-11 2007-10-25 Jiaxin Ge Transparent thin polythiophene films having improved conduction through use of nanomaterials
    US20070278458A1 (en) * 2006-04-13 2007-12-06 Martello Mark T Electrically conductive polymer compositions
    EP2008500A4 (en) * 2006-04-18 2010-01-13 Du Pont High energy-potential bilayer compositions
    US20070278936A1 (en) * 2006-06-02 2007-12-06 Norman Herron Red emitter complexes of IR(III) and devices made with such compounds
    EP2041222B1 (en) * 2006-06-30 2012-12-05 E.I. Du Pont De Nemours And Company Stabilized compositions of conductive polymers and partially-fluorinated acid polymers
    KR101440164B1 (en) * 2006-08-01 2014-09-12 캠브리지 디스플레이 테크놀로지 리미티드 Methods of manufacturing opto-electrical devices
    US8153029B2 (en) 2006-12-28 2012-04-10 E.I. Du Pont De Nemours And Company Laser (230NM) ablatable compositions of electrically conducting polymers made with a perfluoropolymeric acid applications thereof
    US20080166564A1 (en) * 2006-12-28 2008-07-10 Vsevolod Rostovtsev Derivatized monomers for making conductive polymers, and devices made with such polymers
    US8062553B2 (en) * 2006-12-28 2011-11-22 E. I. Du Pont De Nemours And Company Compositions of polyaniline made with perfuoropolymeric acid which are heat-enhanced and electronic devices made therewith
    US20080193773A1 (en) * 2006-12-29 2008-08-14 Che-Hsiung Hsu Compositions of electrically conducting polymers made with ultra-pure fully -fluorinated acid polymers
    US20080191172A1 (en) 2006-12-29 2008-08-14 Che-Hsiung Hsu High work-function and high conductivity compositions of electrically conducting polymers
    WO2008122027A9 (en) * 2007-04-02 2009-01-15 Konarka Technologies Inc Novel electrode
    US20080251768A1 (en) * 2007-04-13 2008-10-16 Che-Hsiung Hsu Electrically conductive polymer compositions
    US20080283800A1 (en) * 2007-05-18 2008-11-20 Che Hsiung Hsu Electrically conductive polymer compositions and films made therefrom
    US8241526B2 (en) * 2007-05-18 2012-08-14 E I Du Pont De Nemours And Company Aqueous dispersions of electrically conducting polymers containing high boiling solvent and additives
    JP2010534739A (en) * 2007-07-27 2010-11-11 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Aqueous dispersion of a conductive polymer containing an inorganic nanoparticles
    DE102007041039A1 (en) * 2007-08-29 2009-03-05 H.C. Starck Gmbh Producing conductive coatings by means of inkjet printing
    JP5337811B2 (en) * 2007-10-26 2013-11-06 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Methods and materials for producing the confinement layer, and devices fabricated using it
    JP4936069B2 (en) * 2007-10-31 2012-05-23 株式会社デンソー Motor controller
    US8183319B2 (en) * 2007-10-31 2012-05-22 Air Products And Chemicals, Inc. Film forming additive formulations of conductive polymers
    JP5243067B2 (en) * 2008-03-10 2013-07-24 日機装株式会社 Conductivity of the conductive polymer improved method
    JP2010192863A (en) * 2008-05-23 2010-09-02 Sumitomo Chemical Co Ltd Organic photoelectric conversion element and method of manufacturing the same
    DE102008032578A1 (en) * 2008-07-11 2010-01-14 H.C. Starck Gmbh A process for the production of electrolytic capacitors
    JP2010080908A (en) * 2008-08-29 2010-04-08 Sumitomo Chemical Co Ltd Organic photoelectric conversion element and fabrication method therefor
    US8268195B2 (en) * 2008-09-29 2012-09-18 Air Products And Chemicals, Inc. Electrically conductive films formed from dispersions comprising polythiophenes and ether containing polymers
    DE102008053589A1 (en) * 2008-10-28 2010-04-29 Bayer Technology Services Gmbh A method for cleaning semiconducting polymers
    US8278405B2 (en) * 2008-12-22 2012-10-02 E I Du Pont De Nemours And Company Vinylphenoxy polymers
    US8785913B2 (en) 2008-12-27 2014-07-22 E I Du Pont De Nemours And Company Buffer bilayers for electronic devices
    US8766239B2 (en) 2008-12-27 2014-07-01 E I Du Pont De Nemours And Company Buffer bilayers for electronic devices
    US8759818B2 (en) 2009-02-27 2014-06-24 E I Du Pont De Nemours And Company Deuterated compounds for electronic applications
    KR101561402B1 (en) 2009-03-12 2015-10-16 이 아이 듀폰 디 네모아 앤드 캄파니 Electrically conductive polymer compositions for coating applications
    CN102369255B (en) 2009-04-03 2014-08-20 E.I.内穆尔杜邦公司 Electroactive materials
    US8845933B2 (en) 2009-04-21 2014-09-30 E I Du Pont De Nemours And Company Electrically conductive polymer compositions and films made therefrom
    KR101581991B1 (en) 2009-04-24 2015-12-31 이 아이 듀폰 디 네모아 앤드 캄파니 Electrically conductive polymer compositions and films made therefrom
    CN107104186A (en) * 2009-09-29 2017-08-29 索尔维美国有限公司 Organic electronic devices, compositions, and methods
    EP2491003A4 (en) 2009-10-19 2015-06-03 Du Pont Triarylamine compounds for electronic applications
    US8937300B2 (en) 2009-10-19 2015-01-20 E I Du Pont De Nemours And Company Triarylamine compounds for use in organic light-emitting diodes
    CN102596950A (en) 2009-10-29 2012-07-18 E.I.内穆尔杜邦公司 Deuterated compounds for electronic applications
    US8617720B2 (en) 2009-12-21 2013-12-31 E I Du Pont De Nemours And Company Electroactive composition and electronic device made with the composition
    US8282861B2 (en) * 2009-12-21 2012-10-09 Che-Hsiung Hsu Electrically conductive polymer compositions
    KR101311933B1 (en) 2009-12-29 2013-09-27 제일모직주식회사 Conductive polymer, conductive polymer composition, film and opto-electronic device using thereof
    US20110291032A1 (en) * 2010-05-27 2011-12-01 Industrial Technology Research Institute Electromagnetic shielding composition, electromagnetic shielding device, anti-electrostatic device and method of manufacturing electromagnetic shielding structure
    CN103493145B (en) 2010-08-20 2017-02-15 罗地亚管理公司 The polymer composition, polymer films, polymer foams gels and polymers, as well as electronic devices containing membranes, gels and foams
    DE102010048032A1 (en) 2010-10-12 2012-04-12 Heraeus Clevios Gmbh Polythiophenes-containing dispersions having a defined content of thiophene monomer
    JP5727038B2 (en) 2010-12-20 2015-06-03 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Compositions for electronics applications
    DE102011003192B4 (en) * 2011-01-26 2015-12-24 Siemens Aktiengesellschaft Semiconductor device and process for its preparation
    JP5764092B2 (en) * 2012-06-04 2015-08-12 Jfeケミカル株式会社 Dispersion and a method for producing a conductive polymer
    JP5955786B2 (en) 2013-01-07 2016-07-20 出光興産株式会社 Conductive polymer composition
    GB201317966D0 (en) 2013-10-10 2013-11-27 Univ Manchester Nanoparticles
    FR3013719B1 (en) * 2013-11-26 2018-01-12 Commissariat Energie Atomique Ink for forming the p layers in organic electronic devices
    US20150367452A1 (en) * 2014-06-24 2015-12-24 Indian Institute Of Technology Kanpur Shadow masks and methods for their preparation and use
    GB2536426A (en) * 2015-03-13 2016-09-21 Cambridge Display Tech Polymer blends for a semiconducting layer of an organic electronic device

    Citations (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0440957A2 (en) 1990-02-08 1991-08-14 Bayer Ag New polythiophene dispersions, their preparation and their use
    JP2003297582A (en) 2002-01-31 2003-10-17 Sumitomo Chem Co Ltd Organic electroluminescent element
    WO2004029128A2 (en) 2002-09-24 2004-04-08 E.I. Du Pont De Nemours And Company Water dispersible polythiophenes made with polymeric acid colloids

    Family Cites Families (186)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US570588A (en) * 1896-11-03 wright
    US3282875A (en) 1964-07-22 1966-11-01 Du Pont Fluorocarbon vinyl ether polymers
    DE2029556A1 (en) 1970-06-16 1971-12-23
    US4358545A (en) 1980-06-11 1982-11-09 The Dow Chemical Company Sulfonic acid electrolytic cell having flourinated polymer membrane with hydration product less than 22,000
    US4433082A (en) 1981-05-01 1984-02-21 E. I. Du Pont De Nemours And Company Process for making liquid composition of perfluorinated ion exchange polymer, and product thereof
    US5378402A (en) 1982-08-02 1995-01-03 Raychem Limited Polymer compositions
    US4552927A (en) * 1983-09-09 1985-11-12 Rockwell International Corporation Conducting organic polymer based on polypyrrole
    FR2588007B1 (en) * 1985-09-30 1988-04-08 Commissariat Energie Atomique Electronically conductive polymers nitrogens, their processes of preparation, electrochromic display cell and electrochemical generator using these polymers
    US4731408A (en) 1985-12-20 1988-03-15 Polaroid Corporation Processable conductive polymers
    US4678596A (en) 1986-05-01 1987-07-07 Rohm And Haas Company Rinse aid formulation
    JPH0678492B2 (en) 1986-11-27 1994-10-05 昭和電工株式会社 Highly conductive polymer composition and a production method thereof
    US4940525A (en) 1987-05-08 1990-07-10 The Dow Chemical Company Low equivalent weight sulfonic fluoropolymers
    US4795543A (en) 1987-05-26 1989-01-03 Transducer Research, Inc. Spin coating of electrolytes
    US5160457A (en) 1987-08-07 1992-11-03 Allied-Signal Inc. Thermally stable forms of electrically conductive polyaniline
    US5069820A (en) 1987-08-07 1991-12-03 Allied-Signal Inc. Thermally stable forms of electrically conductive polyaniline
    JPH01132052A (en) * 1987-08-10 1989-05-24 Nitto Denko Corp Conductive organic polymer battery
    DE3843412A1 (en) 1988-04-22 1990-06-28 Bayer Ag New polythiophene, process for their production and their use
    FR2632979B1 (en) 1988-06-16 1990-09-21 Commissariat Energie Atomique Method of preparing a polymer mixed ionic and electronic conductor and polymers obtained by such process
    DK171065B1 (en) 1988-08-24 1996-05-13 Allied Colloids Ltd Liquid enzyme-containing composition and process for producing same
    US4973391A (en) 1988-08-30 1990-11-27 Osaka Gas Company, Ltd. Composite polymers of polyaniline with metal phthalocyanine and polyaniline with organic sulfonic acid and nafion
    US4933270A (en) 1988-09-26 1990-06-12 Eastman Kodak Company Process for the precipitation of stable colloidal dispersions of base degradable components of photographic systems in the absence of polymeric steric stabilizers
    JPH02160823A (en) 1988-12-15 1990-06-20 Tosoh Corp Production of conductive polymeric complex
    GB8909011D0 (en) * 1989-04-20 1989-06-07 Friend Richard H Electroluminescent devices
    EP0443861B2 (en) * 1990-02-23 2008-05-28 Sumitomo Chemical Company, Limited Organic electroluminescence device
    US5185100A (en) 1990-03-29 1993-02-09 Allied-Signal Inc Conductive polymers formed from conjugated backbone polymers doped with non-oxidizing protonic acids
    BE1008036A3 (en) * 1990-08-30 1996-01-03 Solvay POLYMER BLENDS POLAR AND CONDUCTING POLYMERS dedoped, MIXED THESE PROCESSES OBTAINING AND USE MIXES FOR MAKING ELECTRONIC DEVICES optoelectronic, ELECTROTECHNICAL AND ELECTROMECHANICAL.
    US5258461A (en) 1990-11-26 1993-11-02 Xerox Corporation Electrocodeposition of polymer blends for photoreceptor substrates
    JP3056522B2 (en) 1990-11-30 2000-06-26 三菱レイヨン株式会社 Metal - conducting polymer composite fine particles and manufacturing method thereof
    GB9112141D0 (en) 1991-06-05 1991-07-24 Ici Resins Bv Aqueous coating compositions
    US5463005A (en) 1992-01-03 1995-10-31 Gas Research Institute Copolymers of tetrafluoroethylene and perfluorinated sulfonyl monomers and membranes made therefrom
    JPH05255576A (en) 1992-03-12 1993-10-05 Nippon Chibagaigii Kk Planar heating element and its production
    DE4211461A1 (en) 1992-04-06 1993-10-07 Agfa Gevaert Ag Antistatic plastic parts
    EP0579027A1 (en) * 1992-06-30 1994-01-19 Nitto Denko Corporation Organic polymer solution composition and process for producting electrically conductive organic polymer therefrom
    RU2035803C1 (en) 1992-08-17 1995-05-20 Институт химической физики в Черноголовке РАН Process of manufacture of conductive polymer coat on substrate
    EP0593111B1 (en) 1992-10-14 1998-06-17 AGFA-GEVAERT naamloze vennootschap Antistatic coating composition
    DE69319200D1 (en) 1992-10-14 1998-07-23 Agfa Gevaert Nv Antistatic coating composition
    DE4322130A1 (en) 1993-07-02 1995-01-12 Siemens Ag implantable defibrillator
    DE4334390C2 (en) 1993-10-08 1999-01-21 Nat Science Council A process for the preparation of a processable conductive polymer colloidal
    US5537000A (en) 1994-04-29 1996-07-16 The Regents, University Of California Electroluminescent devices formed using semiconductor nanocrystals as an electron transport media and method of making such electroluminescent devices
    DE19507413A1 (en) 1994-05-06 1995-11-09 Bayer Ag conductive coatings
    EP1271669A3 (en) * 1994-09-06 2005-01-26 Philips Electronics N.V. Electroluminescent device comprising a transparent structured electrode layer made from a conductive polymer
    US5567356A (en) 1994-11-07 1996-10-22 Monsanto Company Emulsion-polymerization process and electrically-conductive polyaniline salts
    US5672699A (en) 1995-09-06 1997-09-30 National Starch And Chemical Investment Holding Corporation Process for preparation of hydrophobic starch derivatives
    DE19543205A1 (en) 1995-11-20 1997-05-22 Bayer Ag Intermediate layer in electroluminescent arrangements containing finely divided inorganic particles
    US5798170A (en) 1996-02-29 1998-08-25 Uniax Corporation Long operating life for polymer light-emitting diodes
    DE19627069A1 (en) 1996-07-05 1998-01-08 Bayer Ag Electroluminescent arrangements using lamellar electrodes
    DE19627071A1 (en) 1996-07-05 1998-01-08 Bayer Ag Electroluminescent arrangements
    WO1998016581A1 (en) 1996-10-15 1998-04-23 E.I. Du Pont De Nemours And Company Compositions containing particles of highly fluorinated ion exchange polymer
    WO1998021755A3 (en) 1996-11-12 1998-10-08 Marie Angelopoulos Patterns of electrically conducting polymers and their application as electrodes or electrical contacts
    DE69715361D1 (en) 1996-12-30 2002-10-17 Centre Nat Rech Scient comprise ionically conductive materials, the salts of perfluorinated amides, and their uses
    DE69835366T2 (en) 1997-03-31 2007-07-19 Daikin Industries, Ltd. A process for the manufacture of perfluorovinylether sulfonic acid derivatives
    US6205016B1 (en) 1997-06-04 2001-03-20 Hyperion Catalysis International, Inc. Fibril composite electrode for electrochemical capacitors
    DE69816601T2 (en) * 1997-11-05 2004-06-03 Koninklijke Philips Electronics N.V. Conjugated polymer in an oxidized state
    US6303238B1 (en) 1997-12-01 2001-10-16 The Trustees Of Princeton University OLEDs doped with phosphorescent compounds
    DE19757542A1 (en) 1997-12-23 1999-06-24 Bayer Ag Screen printing paste for e.g. liquid crystal display
    US6866946B2 (en) 1998-02-02 2005-03-15 Dupont Displays, Inc. High resistance polyaniline useful in high efficiency pixellated polymer electronic displays
    WO1999039395A1 (en) 1998-02-02 1999-08-05 Uniax Corporation Organic diodes with switchable photosensitivity
    US20020038999A1 (en) 2000-06-20 2002-04-04 Yong Cao High resistance conductive polymers for use in high efficiency pixellated organic electronic devices
    JP3444178B2 (en) 1998-02-13 2003-09-08 信越半導体株式会社 Single crystal manufacturing method
    US5952445A (en) 1998-04-09 1999-09-14 Bayer Corporation Water dispersible compounds containing alkoxysilane groups
    US5945476A (en) 1998-04-09 1999-08-31 Bayer Corporation Aqueous two-component coating composition
    US6100324A (en) 1998-04-16 2000-08-08 E. I. Du Pont De Nemours And Company Ionomers and ionically conductive compositions
    DE19824215A1 (en) 1998-05-29 1999-12-02 Bayer Ag Electrochromic arrangement based on poly (3,4-ethylenedioxy-thiophene) derivatives in the electrochromic and ion-storing layer function
    JP3937113B2 (en) 1998-06-05 2007-06-27 日産化学工業株式会社 Organic - inorganic composite conductive sol and its production method
    US6210790B1 (en) 1998-07-15 2001-04-03 Rensselaer Polytechnic Institute Glass-like composites comprising a surface-modified colloidal silica and method of making thereof
    DE19841803A1 (en) 1998-09-12 2000-03-16 Bayer Ag Organic electroluminescent device, i.e. light-emitting diode, has hole-injecting layer of polymeric organic conductor formed by coating from solution or from sub-micron dispersion
    US6097147A (en) 1998-09-14 2000-08-01 The Trustees Of Princeton University Structure for high efficiency electroluminescent device
    US6830828B2 (en) 1998-09-14 2004-12-14 The Trustees Of Princeton University Organometallic complexes as phosphorescent emitters in organic LEDs
    US6187522B1 (en) 1999-03-25 2001-02-13 Eastman Kodak Company Scratch resistant antistatic layer for imaging elements
    DE10018750C2 (en) 1999-04-23 2003-03-27 Kurt Schwabe Inst Fuer Mess Un Contacted solid ion-selective glass electrode and process for their preparation
    US20040217877A1 (en) 1999-05-04 2004-11-04 William Kokonaski Flexible electronic display and wireless communication system
    CN101312235B (en) 1999-05-13 2010-06-09 普林斯顿大学理事会;南加利福尼亚大学 Very high efficiency organic light emitting devices based on electrophosphorescence
    EP1054414B1 (en) 1999-05-20 2003-03-12 Agfa-Gevaert Method for patterning a layer of conductive polymer
    US6340496B1 (en) * 1999-05-20 2002-01-22 Agfa-Gevaert Method for patterning a layer of conductive polymers
    US20020099119A1 (en) 1999-05-27 2002-07-25 Bradley D. Craig Water-borne ceramer compositions and antistatic abrasion resistant ceramers made therefrom
    KR100302326B1 (en) 1999-06-09 2001-09-22 윤덕용 Inorganic-organic Copolymer Using Polyvinylalcohol-Silane Copuling Reagent and Preparation Method Thereof
    US6620494B2 (en) 1999-07-03 2003-09-16 Ten Cate Enbi B.V. Conductive roller
    US6593690B1 (en) 1999-09-03 2003-07-15 3M Innovative Properties Company Large area organic electronic devices having conducting polymer buffer layers and methods of making same
    JP3656244B2 (en) 1999-11-29 2005-06-08 株式会社豊田中央研究所 High durability solid polymer electrolyte and electrode using the high durability solid polymer electrolyte - electrolyte assembly and its electrodes - an electrochemical device using the electrolyte assembly
    KR100794975B1 (en) 1999-12-01 2008-01-16 더 트러스티즈 오브 프린스턴 유니버시티 Complexes of form l2mx as phosphorescent dopants for organic leds
    US6821645B2 (en) 1999-12-27 2004-11-23 Fuji Photo Film Co., Ltd. Light-emitting material comprising orthometalated iridium complex, light-emitting device, high efficiency red light-emitting device, and novel iridium complex
    US6324091B1 (en) 2000-01-14 2001-11-27 The Regents Of The University Of California Tightly coupled porphyrin macrocycles for molecular memory storage
    JP2001270999A (en) 2000-01-19 2001-10-02 Mitsubishi Rayon Co Ltd Crosslinkable electric conductive composition, water resistant electric conductor and process for manufacturing the same
    KR20010095437A (en) 2000-03-30 2001-11-07 윤덕용 Organic Electro luminescent Devices Using Emitting material/Clay Nano Complex Composite
    JP2001325831A (en) 2000-05-12 2001-11-22 Bando Chem Ind Ltd Metal colloid solution, conductive ink, conductive coating and conductive coating forming base film
    US20020036291A1 (en) 2000-06-20 2002-03-28 Parker Ian D. Multilayer structures as stable hole-injecting electrodes for use in high efficiency organic electronic devices
    US6632472B2 (en) 2000-06-26 2003-10-14 Agfa-Gevaert Redispersable latex comprising a polythiophene
    US6670645B2 (en) 2000-06-30 2003-12-30 E. I. Du Pont De Nemours And Company Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds
    JP2002082082A (en) 2000-09-07 2002-03-22 Matsushita Refrig Co Ltd Odor sensor and its manufacturing method
    JP4154139B2 (en) 2000-09-26 2008-09-24 キヤノン株式会社 The light-emitting element
    JP4154140B2 (en) 2000-09-26 2008-09-24 キヤノン株式会社 Metal coordination compounds
    US7662265B2 (en) 2000-10-20 2010-02-16 Massachusetts Institute Of Technology Electrophoretic assembly of electrochemical devices
    EP1433217A2 (en) 2001-07-27 2004-06-30 A123 Systems, Inc. Battery structures, self-organizing structures and related methods
    US6515314B1 (en) 2000-11-16 2003-02-04 General Electric Company Light-emitting device with organic layer doped with photoluminescent material
    JP4095894B2 (en) 2000-11-22 2008-06-04 バイエル・ベタイリグングスフェアヴァルトゥング・ゴスラー・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングBayer Beteiligungsverwaltung Goslar GmbH Dispersible polymer powders
    DE10103416A1 (en) 2001-01-26 2002-08-01 Bayer Ag Electroluminescent arrangements
    US6599631B2 (en) 2001-01-26 2003-07-29 Nanogram Corporation Polymer-inorganic particle composites
    EP1231251A1 (en) 2001-02-07 2002-08-14 Agfa-Gevaert Thin film inorganic light emitting diode
    US7244797B2 (en) 2001-02-08 2007-07-17 Asahi Kasei Kabushiki Kaisha Organic domain/inorganic domain complex materials and use thereof
    US6756474B2 (en) 2001-02-09 2004-06-29 E. I. Du Pont De Nemours And Company Aqueous conductive dispersions of polyaniline having enhanced viscosity
    DE10126860C2 (en) 2001-06-01 2003-05-28 Siemens Ag An organic field effect transistor, process for its preparation and use for the construction of integrated circuits
    US6875523B2 (en) 2001-07-05 2005-04-05 E. I. Du Pont De Nemours And Company Photoactive lanthanide complexes with phosphine oxides, phosphine oxide-sulfides, pyridine N-oxides, and phosphine oxide-pyridine N-oxides, and devices made with such complexes
    JP2003023909A (en) 2001-07-10 2003-01-28 Suga Marin Mechanic:Kk Artificial fish-breeding reef having core obtained by bundling pipes
    WO2003006537A1 (en) 2001-07-13 2003-01-23 E.I. Du Pont De Nemours And Company Process for dissolution of highly fluorinated ion-exchange polymers
    US6777515B2 (en) 2001-07-13 2004-08-17 I. Du Pont De Nemours And Company Functional fluorine-containing polymers and ionomers derived therefrom
    JP2004536133A (en) 2001-07-18 2004-12-02 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Device produced from luminescent lanthanide complexes and such complexes have a imine ligand
    US6627333B2 (en) 2001-08-15 2003-09-30 Eastman Kodak Company White organic light-emitting devices with improved efficiency
    US7112368B2 (en) 2001-11-06 2006-09-26 E. I. Du Pont De Nemours And Company Poly(dioxythiophene)/poly(acrylamidoalkyslufonic acid) complexes
    US7166368B2 (en) 2001-11-07 2007-01-23 E. I. Du Pont De Nemours And Company Electroluminescent platinum compounds and devices made with such compounds
    JP4049744B2 (en) 2001-12-04 2008-02-20 アグフア−ゲヴエルト,ナームローゼ・フエンノートシヤツプ Method for producing an aqueous or non-aqueous solution or dispersion of a polythiophene or thiophene copolymer
    EP1326260A1 (en) 2001-12-11 2003-07-09 Agfa-Gevaert Material for making a conductive pattern
    JP2003187983A (en) 2001-12-17 2003-07-04 Ricoh Co Ltd Organic el transistor
    EP1321483A1 (en) 2001-12-20 2003-06-25 Agfa-Gevaert 3,4-alkylenedioxythiophene compounds and polymers thereof
    US20030141487A1 (en) 2001-12-26 2003-07-31 Eastman Kodak Company Composition containing electronically conductive polymer particles
    EP2306789A1 (en) 2001-12-26 2011-04-06 E. I. du Pont de Nemours and Company Phenyl-pyridine compounds
    JP2003217862A (en) 2002-01-18 2003-07-31 Honda Motor Co Ltd Organic electroluminescent element
    US6706963B2 (en) 2002-01-25 2004-03-16 Konarka Technologies, Inc. Photovoltaic cell interconnection
    US6923881B2 (en) 2002-05-27 2005-08-02 Fuji Photo Film Co., Ltd. Method for producing organic electroluminescent device and transfer material used therein
    JP4288895B2 (en) 2002-06-04 2009-07-01 コニカミノルタホールディングス株式会社 A method of manufacturing an organic electroluminescence
    US20040004433A1 (en) 2002-06-26 2004-01-08 3M Innovative Properties Company Buffer layers for organic electroluminescent devices and methods of manufacture and use
    JP3606855B2 (en) 2002-06-28 2005-01-05 ドン ウン インターナショナル カンパニー リミテッド The method of producing a carbon nano particles
    US7071289B2 (en) * 2002-07-11 2006-07-04 The University Of Connecticut Polymers comprising thieno [3,4-b]thiophene and methods of making and using the same
    JP4077675B2 (en) 2002-07-26 2008-04-16 エイチ・シー・スタルク・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングH.C.Starck Gmbh Poly (3,4-dialkoxythiophene) and an aqueous dispersion containing a complex of the polyanion and a method for producing
    US6963005B2 (en) 2002-08-15 2005-11-08 E. I. Du Pont De Nemours And Company Compounds comprising phosphorus-containing metal complexes
    US7118836B2 (en) 2002-08-22 2006-10-10 Agfa Gevaert Process for preparing a substantially transparent conductive layer configuration
    US20040092700A1 (en) 2002-08-23 2004-05-13 Che-Hsiung Hsu Methods for directly producing stable aqueous dispersions of electrically conducting polyanilines
    US7307276B2 (en) 2002-08-23 2007-12-11 Agfa-Gevaert Layer configuration comprising an electron-blocking element
    US6977390B2 (en) 2002-08-23 2005-12-20 Agfa Gevaert Layer configuration comprising an electron-blocking element
    JP2004082395A (en) 2002-08-23 2004-03-18 Eamex Co Method for forming laminate and laminate
    JP4975237B2 (en) 2002-08-27 2012-07-11 パナソニック株式会社 Preparation and solid electrolytic capacitor using the same conductive composition
    JP4135449B2 (en) 2002-09-20 2008-08-20 日本ケミコン株式会社 Conductive polymer polymerization oxidant
    US7462298B2 (en) 2002-09-24 2008-12-09 E.I. Du Pont De Nemours And Company Water dispersible polyanilines made with polymeric acid colloids for electronics applications
    US7371336B2 (en) 2002-09-24 2008-05-13 E.I. Du Pont Nemours And Company Water dispersible polyanilines made with polymeric acid colloids for electronics applications
    US7390438B2 (en) 2003-04-22 2008-06-24 E.I. Du Pont De Nemours And Company Water dispersible substituted polydioxythiophenes made with fluorinated polymeric sulfonic acid colloids
    EP2341118A1 (en) 2002-09-24 2011-07-06 E. I. du Pont de Nemours and Company Electrically conducting organic polymer/nanoparticle composites and methods for use thereof
    US7317047B2 (en) 2002-09-24 2008-01-08 E.I. Du Pont De Nemours And Company Electrically conducting organic polymer/nanoparticle composites and methods for use thereof
    US6717358B1 (en) 2002-10-09 2004-04-06 Eastman Kodak Company Cascaded organic electroluminescent devices with improved voltage stability
    KR100525977B1 (en) 2002-11-19 2005-11-03 나노캠텍주식회사 Method for producing 3,4-alkylenedioxythiophenes and 3,4-dialkoxythiophenes
    US6793197B2 (en) 2003-01-30 2004-09-21 Fisher Controls International, Inc. Butterfly valve
    US6867281B2 (en) 2003-03-26 2005-03-15 The United States Of America As Represented By The Secretary Of The Navy Highly conducting and transparent thin films formed from new fluorinated derivatives of 3,4-ethylenedioxythiophene
    US6858157B2 (en) * 2003-04-17 2005-02-22 Vnaderbilt University Compositions with nano-particle size diamond powder and methods of using same for transferring heat between a heat source and a heat sink
    WO2004105150A1 (en) 2003-05-19 2004-12-02 E.I. Dupont De Nemours And Company Hole transport composition
    US7318982B2 (en) 2003-06-23 2008-01-15 A123 Systems, Inc. Polymer composition for encapsulation of electrode particles
    DE112004001169T5 (en) 2003-06-27 2006-06-01 E.I. Du Pont De Nemours And Co., Wilmington Compounds containing trifluorostyrene and their use in polymer electrolyte membranes
    DE10331673A1 (en) 2003-07-14 2005-02-10 H.C. Starck Gmbh Polythiophene with Alkylenoxythiathiophen units in electrolytic capacitors
    JP4983021B2 (en) 2003-09-08 2012-07-25 住友金属鉱山株式会社 The organic el element using it with transparent conductive laminate and a process for their preparation
    DE10343873A1 (en) 2003-09-23 2005-04-21 Starck H C Gmbh A process for the purification of thiophenes
    JP4381080B2 (en) 2003-09-29 2009-12-09 大日本印刷株式会社 The organic electroluminescent device and a manufacturing method thereof
    US7618704B2 (en) 2003-09-29 2009-11-17 E.I. Du Pont De Nemours And Company Spin-printing of electronic and display components
    US7105237B2 (en) 2003-10-01 2006-09-12 The University Of Connecticut Substituted thieno[3,4-B]thiophene polymers, method of making, and use thereof
    US20050209392A1 (en) 2003-12-17 2005-09-22 Jiazhong Luo Polymer binders for flexible and transparent conductive coatings containing carbon nanotubes
    US20050175861A1 (en) 2004-02-10 2005-08-11 H.C. Starck Gmbh Polythiophene compositions for improving organic light-emitting diodes
    DE102004006583A1 (en) 2004-02-10 2005-09-01 H.C. Starck Gmbh Polythiophenformulierungen to improve organic light emitting diodes
    US7960587B2 (en) 2004-02-19 2011-06-14 E.I. Du Pont De Nemours And Company Compositions comprising novel compounds and electronic devices made with such compositions
    US7365230B2 (en) 2004-02-20 2008-04-29 E.I. Du Pont De Nemours And Company Cross-linkable polymers and electronic devices made with such polymers
    US7112369B2 (en) 2004-03-02 2006-09-26 Bridgestone Corporation Nano-sized polymer-metal composites
    DE102004010811B4 (en) 2004-03-05 2006-06-29 H.C. Starck Gmbh Composition useful in article of manufacture e.g. electroluminescent arrangement comprises polythiophenes; polymer that is different from polythiophene; and polymer selected from partially fluorinated polymer and/or perfluorinated polymer
    US7351358B2 (en) 2004-03-17 2008-04-01 E.I. Du Pont De Nemours And Company Water dispersible polypyrroles made with polymeric acid colloids for electronics applications
    US7338620B2 (en) 2004-03-17 2008-03-04 E.I. Du Pont De Nemours And Company Water dispersible polydioxythiophenes with polymeric acid colloids and a water-miscible organic liquid
    US7250461B2 (en) 2004-03-17 2007-07-31 E. I. Du Pont De Nemours And Company Organic formulations of conductive polymers made with polymeric acid colloids for electronics applications, and methods for making such formulations
    WO2005090446A1 (en) 2004-03-18 2005-09-29 Ormecon Gmbh A composition comprising a conductive polymer in colloidal form and carbon
    US20050222333A1 (en) 2004-03-31 2005-10-06 Che-Hsiung Hsu Aqueous electrically doped conductive polymers and polymeric acid colloids
    US7455793B2 (en) 2004-03-31 2008-11-25 E.I. Du Pont De Nemours And Company Non-aqueous dispersions comprising electrically doped conductive polymers and colloid-forming polymeric acids
    US7354532B2 (en) 2004-04-13 2008-04-08 E.I. Du Pont De Nemours And Company Compositions of electrically conductive polymers and non-polymeric fluorinated organic acids
    US7378040B2 (en) 2004-08-11 2008-05-27 Eikos, Inc. Method of forming fluoropolymer binders for carbon nanotube-based transparent conductive coatings
    US20060051401A1 (en) 2004-09-07 2006-03-09 Board Of Regents, The University Of Texas System Controlled nanofiber seeding
    US7211824B2 (en) 2004-09-27 2007-05-01 Nitto Denko Corporation Organic semiconductor diode
    US7388235B2 (en) 2004-09-30 2008-06-17 The United States Of America As Represented By The Secretary Of The Navy High electron mobility transistors with Sb-based channels
    US7569158B2 (en) 2004-10-13 2009-08-04 Air Products And Chemicals, Inc. Aqueous dispersions of polythienothiophenes with fluorinated ion exchange polymers as dopants
    US7838688B2 (en) 2004-12-30 2010-11-23 E.I. Du Pont De Nemours And Company Derivatized 3,4-Alkylenedioxythiophene monomers, methods of making them, and use thereof
    US7985490B2 (en) 2005-02-14 2011-07-26 Samsung Mobile Display Co., Ltd. Composition of conducting polymer and organic opto-electronic device employing the same
    US7593004B2 (en) 2005-06-02 2009-09-22 Eastman Kodak Company Touchscreen with conductive layer comprising carbon nanotubes
    US7645497B2 (en) 2005-06-02 2010-01-12 Eastman Kodak Company Multi-layer conductor with carbon nanotubes
    WO2007002683A3 (en) 2005-06-27 2007-09-20 Du Pont Electrically conductive polymer compositions
    US7727421B2 (en) 2005-06-27 2010-06-01 E. I. Du Pont De Nemours And Company Dupont Displays Inc Electrically conductive polymer compositions
    KR101294892B1 (en) 2005-06-27 2013-08-09 이 아이 듀폰 디 네모아 앤드 캄파니 Electrically Conductive Polymer Compositions
    JP2008547186A (en) 2005-06-28 2008-12-25 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Bilayer anode
    CN101208369B (en) 2005-06-28 2013-03-27 E.I.内穆尔杜邦公司 High work function transparent conductor
    WO2007002740A3 (en) 2005-06-28 2009-04-16 Du Pont Buffer compositions
    US8216680B2 (en) 2006-02-03 2012-07-10 E I Du Pont De Nemours And Company Transparent composite conductors having high work function
    EP2008500A4 (en) 2006-04-18 2010-01-13 Du Pont High energy-potential bilayer compositions
    US8153029B2 (en) 2006-12-28 2012-04-10 E.I. Du Pont De Nemours And Company Laser (230NM) ablatable compositions of electrically conducting polymers made with a perfluoropolymeric acid applications thereof
    US20080251768A1 (en) 2007-04-13 2008-10-16 Che-Hsiung Hsu Electrically conductive polymer compositions
    US8241526B2 (en) 2007-05-18 2012-08-14 E I Du Pont De Nemours And Company Aqueous dispersions of electrically conducting polymers containing high boiling solvent and additives
    US20080283800A1 (en) 2007-05-18 2008-11-20 Che Hsiung Hsu Electrically conductive polymer compositions and films made therefrom
    JP2009185739A (en) 2008-02-07 2009-08-20 Toyota Motor Corp Fuel reforming device

    Patent Citations (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0440957A2 (en) 1990-02-08 1991-08-14 Bayer Ag New polythiophene dispersions, their preparation and their use
    JP2003297582A (en) 2002-01-31 2003-10-17 Sumitomo Chem Co Ltd Organic electroluminescent element
    WO2004029128A2 (en) 2002-09-24 2004-04-08 E.I. Du Pont De Nemours And Company Water dispersible polythiophenes made with polymeric acid colloids

    Also Published As

    Publication number Publication date Type
    US7390438B2 (en) 2008-06-24 grant
    WO2004094501A3 (en) 2005-03-24 application
    US8641926B2 (en) 2014-02-04 grant
    WO2004094501A2 (en) 2004-11-04 application
    EP1615971A2 (en) 2006-01-18 application
    US20080248314A1 (en) 2008-10-09 application
    EP1615971B1 (en) 2009-06-03 grant
    US20040254297A1 (en) 2004-12-16 application
    KR20060010756A (en) 2006-02-02 application

    Similar Documents

    Publication Publication Date Title
    US20060237695A1 (en) Copolymers of soluble poly(thiophenes) with improved electronic performance
    US7071289B2 (en) Polymers comprising thieno [3,4-b]thiophene and methods of making and using the same
    US20120138913A1 (en) Electrically conductive nanostructures, method for making such nanostructures, electrically conductive polumer films containing such nanostructures, and electronic devices containing such films
    US20030118829A1 (en) Poly(dioxythiophene)/poly(acrylamidoalkylsulfonic acid) complexes
    Kirchmeyer et al. Scientific importance, properties and growing applications of poly (3, 4-ethylenedioxythiophene)
    US20040074779A1 (en) Polymeric compositions comprising thieno[3,4-b]thiophene, method of making, and use thereof
    US20050175861A1 (en) Polythiophene compositions for improving organic light-emitting diodes
    US20060236531A1 (en) Electrolyte capacitors having a polymeric outer layer and process for their production
    US7563392B1 (en) Organic conductive compositions and structures
    US20080283800A1 (en) Electrically conductive polymer compositions and films made therefrom
    US20040152832A1 (en) Aqueous dispersion containing a complex of poly(3,4-dialkoxythiophene) and a polyanion and method for producing the same
    US20050019976A1 (en) Non-vacuum methods for the fabrication of organic semiconductor devices
    US20050053801A1 (en) Transparent electrode for electro-optical structures
    US20080213594A1 (en) Laser (230nm) ablatable compositions of electrically conducting polymers made with a perfluoropolymeric acid applications thereof
    US20070069185A1 (en) Electrically conductive polymer compositions
    US20030006401A1 (en) Compositions produced by solvent exchange methods and uses thereof
    US20060292362A1 (en) Bilayer anode
    US20060289843A1 (en) Buffer compositions
    US20080166566A1 (en) Process for forming an organic light-emitting diode and devices made by the process
    US20070298530A1 (en) Process for making an organic electronic device
    US20080023676A1 (en) Stabilized compositions of conductive polymers and partially fluorinated acid polymers
    US20070278453A1 (en) Electrically conductive polymers and method of making electrically conductive polymers
    WO2007002683A2 (en) Electrically conductive polymer compositions
    US20050151122A1 (en) Dispersions and films comprising conducting polymer for optoelectronic devices
    US20090230361A1 (en) Modified planarizng agents and devices

    Legal Events

    Date Code Title Description
    AK Designated contracting states:

    Kind code of ref document: A2

    Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

    17P Request for examination filed

    Effective date: 20051004

    AX Request for extension of the european patent to

    Extension state: AL HR LT LV MK

    RIN1 Inventor (correction)

    Inventor name: LECLOUX, DANIEL, DAVID

    Inventor name: ZHANG, CHI

    Inventor name: KIM, SUNGHAN

    Inventor name: CAO, YONG

    Inventor name: MACPHERSON, CHARLES DOUGLAS

    Inventor name: LI, HUAWEN

    Inventor name: SKULASON, HJALTI

    Inventor name: HSU, CHE-HSIUNG

    RBV Designated contracting states (correction):

    Designated state(s): DE GB

    DAX Request for extension of the european patent (to any country) deleted
    AK Designated contracting states:

    Kind code of ref document: B1

    Designated state(s): DE GB

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    REF Corresponds to:

    Ref document number: 602004021370

    Country of ref document: DE

    Date of ref document: 20090716

    Kind code of ref document: P

    26 Opposition filed

    Opponent name: H.C. STARCK CLEVIOS GMBH

    Effective date: 20100302

    RIC2 Classification (correction)

    Ipc: B82Y 30/00 20110101AFI20120309BHEP

    R26 Opposition filed (correction)

    Opponent name: HERAEUS PRECIOUS METALS GMBH & CO. KG

    Effective date: 20100302

    R26 Opposition filed (correction)

    Opponent name: HERAEUS PRECIOUS METALS GMBH & CO. KG

    Effective date: 20100302

    R26 Opposition filed (correction)

    Opponent name: HERAEUS PRECIOUS METALS GMBH & CO. KG

    Effective date: 20100302

    RAP2 Transfer of rights of an ep granted patent

    Owner name: E. I. DU PONT DE NEMOURS AND COMPANY

    AK Designated contracting states:

    Kind code of ref document: B2

    Designated state(s): DE GB

    27A Maintained as amended

    Effective date: 20171227

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R102

    Ref document number: 602004021370

    Country of ref document: DE

    PGFP Postgrant: annual fees paid to national office

    Ref country code: GB

    Payment date: 20180329

    Year of fee payment: 15

    PGFP Postgrant: annual fees paid to national office

    Ref country code: DE

    Payment date: 20180410

    Year of fee payment: 15